Supporting Information

© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2005

1

Cationic P–S–X cages (X = Br, I)

M. Gonsior[a], I. Krossing*, [b], E. Matern[a]

[a] Universität Karlsruhe, Institut für Anorganische Chemie

Engesserstr. Geb. 30.45, 76128 Karlsruhe

e-mail: gonsior@chemie.uni-karlsruhe.de

[b] Ecole Polytechnique Fédérale de Lausanne (EPFL)

Laboratory of Inorganic and Coordination Chemistry (LCIC), ISIC-BCH

1015 Lausanne, Switzerland

e-mail: ingo.krossing@epfl.ch

2

S-1. Supplemental NMR section: Overview Specta

P5S3Br2+

PBr3

P4S3

Figure 0. 31P NMR spectrum of the in situ prepared P5S3Br2

+[Al(OR)4]– (1a) salt recorded at

193K in CD2Cl2 showing the broad signals of exchanging coordinated P4S3 and PBr3.

100110120130140150160170180190200210220230240250260

(ppm)

3

Fig. A. 31P NMR spectrum of the in situ prepared P5S3Br2+[Al(OR)4]– (E1a) salt recorded at

193K in CD2Cl2 from +265 ppm to +95 ppm. At the bottom the attempted simulation. The broad signal at 228 ppm belongs to PBr3 (see main text).

4

406080100120140160180200220240260

(ppm) Fig. B. 31P NMR spectrum of in situ prepared P5S3I2

+[Al(OR)4]– salt (1b) recorded at 223K in CD2Cl2 (top) and its simulation (bottom). The signal at d = 75.1 (q, 2JPP = 62.6 Hz), which is not present in the simulated spectrum, belongs to the apical phosphorus atom of P4S3 in Ag(P4S3)x

+.

5

-300-260-220-180-140-100-60-202060100140180220

P5S3I2+

P5S2I2+

P4S4I+

?

?

?

??

??

?

?

??

??

??

?

Ag(P4S3)x+

-300-260-220-180-140-100-60-202060100140180220

P5S3I2+

P5S2I2+

P4S4I+

?

?

?

??

??

?

?

??

??

??

?

-300-260-220-180-140-100-60-202060100140180220

P5S3I2+

P5S2I2+

P4S4I+

?

?

?

??

??

?

?

??

??

??

?

Ag(P4S3)x+

Figure C. 31P NMR spectrum of the in situ reaction between P4S3, PI3 and Ag[Al(OR)]4 recorded at 233K in CD2Cl2 showing the mixture of

P5S3I2+[Al(OR)4]– (1b), P5S2I2

+[Al(OR)4]– (2b) and P4S4I+[Al(OR)4]– (3b). The signals of all three compounds were simulated below the

experimental spectrum. The doublet at d = -125.2 (2JPP = 69.3 Hz) was assigned to P4S3 in [Ag(P4S3)x]+, however it was not simulated.

Simulation of the mixture

6

60708090100110120130140150160170180190200210220230240250260

(ppm) Fig. D. 31P NMR spectrum of in situ reaction between P4S3, PI3 and Ag[Al(OR)]4 recorded at 233K in CD2Cl2 (top) containing P5S3I2

+[Al(OR)4]– (1b), P5S2I2

+[Al(OR)4]– (2b) and P4S4I+[Al(OR)4]– (3a, its simulation at the bottom). The spectrum is plotted only in the range of the signals of (3a) (for the whole spectrum see above).

P4S4I+ Simulation

7

-280-240-200-160-120-80-4004080

(ppm)

Fig. E. The 31P NMR spectrum of the isolated crystals of P5S2I2+[Al(OR)4]– (2b) recorded at 243K in CD2Cl2 (top) and its simulation (bottom)

8

-260-220-180-140-100-60-202060100140180220

(ppm)

120130140150160170180190200210220230240250260270

(ppm) Figure F. 31P NMR spectra of the isolated crystalline material from the reaction between P4S3,

PBr3 and Ag[Al(OR)]4 recorded at 243K (CD2Cl2) (top) containing P5S2Br2+[Al(OR)4]– (2a +

simulation) and P4S4Br+[Al(OR)4]– (3a). The second spectrum is the section of the resonances

of 3a with their simulation. The sharp singlet at d = +225 (s) belongs probably to P6Br6 (or

PBr3). Other phosphorus signals account for small impurities.

P5S2Br2+ Simulation

P4S4Br+ Simulation

Mixture of P4S4Br+ and P5S2Br2+

9

Details to the NMR spectra

Compound 1b: TITLE: Gonsior M28-5 CD2Cl2 gons.406 223K AC250 Verb1b P5S3I2+ OptS 987 g406optS.987 ISO-VALUE RESONANCE FREQUENCY 31 26476.8949 31 17078.6881 31 14811.4410 31 6489.7114 31 4525.8663 COUPLINGS SCALAR DIPOLAR 1 2 74.2441 0.0000 1 3 36.0985 0.0000 1 4 28.8741 0.0000 1 5 54.5809 0.0000 2 3 -190.9907 0.0000 2 4 41.6050 0.0000 2 5 -344.8276 0.0000 3 4 -206.3145 0.0000 3 5 128.7160 0.0000 4 5 -283.2161 0.0000 GLOBAL LINEWIDTH : 12.0000 Standard Deviation of Measurements = 0.212938 R-Factor ( % ) = 1.672407 Fragm. Parameter type Initial Parameter Best Parameter Standard No. Vector Vector Deviation ----------------------------------------------------------------- 1 F( 1 ) 26476.89490 26476.89928 0.09568 1 F( 2 ) 17078.68810 17078.66164 0.06345 1 F( 3 ) 14811.44100 14811.46283 0.06903 1 F( 4 ) 6489.71140 6489.66965 0.06976 1 F( 5 ) 4525.86630 4525.99553 0.06005 1 J( 1, 2 ) 74.24410 74.25033 0.08782 1 J( 1, 3 ) 36.09850 36.10309 0.08605 1 J( 1, 4 ) 28.87410 28.88779 0.08248 1 J( 1, 5 ) 54.58090 54.58248 0.08368 1 J( 2, 3 ) -190.99070 -190.98739 0.08611 1 J( 2, 4 ) 41.60500 41.60633 0.08406 1 J( 2, 5 ) -344.82760 -344.82183 0.08910 1 J( 3, 4 ) -206.31450 -206.31312 0.08840 1 J( 3, 5 ) 128.71600 128.71499 0.08786 1 J( 4, 5 ) -283.21610 -283.20001 0.09488

10

= P5S3I2+

257.0258.0259.0260.0261.0262.0263.0264.0265.0266.0267.0

Experiment

Simulation

= P5S3I2+

163.0164.0165.0166.0167.0168.0169.0170.0171.0172.0173.0

Experiment

Simulation

11

= P5S3I2+

141.0142.0143.0144.0145.0146.0147.0148.0149.0150.0

Experiment

Simulation

= P5S3I2+

59.060.061.062.063.064.065.066.067.068.069.0

Experiment

Simulation

12

Compound 1a

= P5S3I2+

40.041.042.043.044.045.046.047.048.049.0

Experiment

Simulation

100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 (ppm)

= P5S3Br2+

Coordinated PBr3 (Silver complex)

Experimental spectrum at 203 K

13

= P5S3Br2+

257.1 ppm, PD

(ppm)

253.0254.0255.0256.0257.0258.0259.0260.0261.0

Experimental spectrum at 203 K

159 ppm, PC

150155160165

= P5S3Br2+ Experimental spectrum at 203 K

14

= P5S3Br2+

110, 113, 117 ppm, PA, B, E104106108110112114116118120122124

GONSIOR S3-1 CD2CL2 31P[1H] 203K

Experimental spectrum at 203 K

= aaproximately 113.5 ppm.

15

IR spectroscopy

Experimental IR Spectrum and Simulation of P5S2I2

+[Al(OR)4]–

* - Anion? - P5S2I2

+

Experiment

P5S2I2+[Al(OR)4]–

simulation

[Al(OR)4]–

simulation

*

*

**

*

*

*

*

**

*

*

*

**

**

*

** ?

?

?

?

?

??

??

*

*

**

*

*

*

*

**

*

*

*

**

**

*

** ?

?

?

?

?

??

??

200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400

Fig. G. Experimental (top) and simulated spectra of 2b (middle) and the isolated [Al(OR)4]– anion (bottom). The frequencies of P5S2I2

+ and [Al(OR)4]– for the simulation were calculated at the BP/SVP level. The cation bands are collected in Tab. 3.

16

Experimental IR Spectrum and Simulation of the P5S2Br2+[Al(OR)4]– and P4S4Br+[Al(OR)4]–

Mixture

Experiment

Simulation of theexperimental spectrum

P4S4Br+[Al(OR)4]–

simulation

P5S2Br2+[Al(OR)4]–

simulation

200 300 400 500 600 700 800 900 1000 1100 1200 1300

[Al(OR)4]– simulation

*

*

**

**

**

*

*

*

*

*

*

*

**

? - P4S4Br+[Al(OR)4]–

? - P5S2Br2+[Al(OR)4]–

- [Al(OR)4]–*- [(RO)3Al–F–Al(OR)3]–?

?

?

*

*

*

?

???

??

?

??

?

?

?

??

Experiment

Simulation of theexperimental spectrum

P4S4Br+[Al(OR)4]–

simulation

P5S2Br2+[Al(OR)4]–

simulation

200 300 400 500 600 700 800 900 1000 1100 1200 1300200 300 400 500 600 700 800 900 1000 1100 1200 1300

[Al(OR)4]– simulation

*

*

**

**

**

*

*

*

*

*

*

*

**

? - P4S4Br+[Al(OR)4]–

? - P5S2Br2+[Al(OR)4]–

- [Al(OR)4]–*- [(RO)3Al–F–Al(OR)3]–?

?

?

*

*

*

?

???

??

?

??

?

?

?

??

Fig. H. Experimental spectrum of a mixture of 2a and 3a (top) and its simulation. Other three spectra are simulations of each salt from the mixture and the [Al(OR)4)]– anion separate. The vibrations of cations and anion are marked by symbols. Two other bands (at 638 and 863 cm-1) that are not present in the simulation are due to partial decomposition of the anion and belong to the fluorine bridged [(RO)3Al–F–Al(OR)3]– anion.

17

Tab. A. Experimental and calculated frequencies of 2b. Grey colored fields in the table denote cation vibrations. Bands assigned to the anion in 2b are compared to the anion vibrations in

CS2Br3+[Al(OR)4]–. All calculated cation bands are listed in the separate row (right).

2b Assignment of 2b Anion vibrations in CS2Br3

+[Al(OR)4]– Complete calculated

vibrations of 2b cm–1 intensity cm–1 intensity cm–1 intensity cm–1 intensity 215 w 215 w 42 (0) 229 w 202 vw(7) 49 (0) 286 w 284 w 63 vw(1) 290 m 269 m(15) 92 vw(1) 315 m 314 w 130 vw(1) 331 w 330 vw 135 (0) 335 m 317 m(19) 174 vw(1) 372 w 202 vw(7) 404 m 365/366 m(10+7) 269 m(15) 427 s 384 s(58)

365 to 427

broad 273 (0)

436 sh 391 m(10) 317 m(19) 442 sh 423/433 m(12+18) 324 vw(4) 444 s 445 m 333 vw(3) 483 m 458 w(8) 365 m(10) 491 w 465 vw(4) 366 w(7) 536 s 537 mw 384 s(58) 561 m 561 mw 391 m(10) 571 m 571 w 423 m(12) 727 vs 728 s 433 m(18) 755 m 755 w 458 w(8) 831 m 832 m 465 vw(4) 972 vs 973 vs 1079 w 1075 w (sh)

- - 1133 m (sh) 1161 w 1169 ms 1219 vs 1219 vs 1247 vs 1242 vs 1275 vs 1276 vs 1299 vs 1301 s 1353 s 1353 ms

18

Tab. B. Experimental and assigned calculated frequencies of 2a and 3a. The colored fields in the table denotes cation vibrations and have following codes: light grey - 2a, dark grey - 3a.

Bands assigned to the anion in 2a, 3a are compared to the anion vibrations in CS2Br3

+[Al(OR)4]–. All calculated cation bands of 2a and 3a are listed in two separate rows (right).

2a and 3a Assignment

of 2a Assignment of

3a Anion vibrations in CS2Br3

+[Al(OR)4]–

Complete calculated

vibrations of 2a cation

Complete calculated

vibrations of 3a cation

cm–1 Int. cm–1 Int. cm–1 Int. cm–1 Int. cm–1 Int. cm–1 Int. 216 w 215 w 53 0 68 0 230 vw 203 w(5) 57 0 94 0 235 vw 214 w(3) 94 vw(1) 142 0 285 m 284 w 110 vw(1) 150 vw(1) 315 s 314 w 151 0 173 0 331 w 330 vw 169 0 208 vw(2) 346 m 323 m(11) 176 vw(1) 214 vw(3) 375 m 358 m(17) 203 vw(5) 221 vw(2) 392 vs 370 m(21) 273 0 64 vw(2) 409 s 390 m(17)

365 to 427 broad 278 w(7) 301 vw(2)

422 m 419 m(17) 323 w(11) 310 vw(1) 437 s 427 w(10) 327 vw(2) 329 vw(1) 444 s 445 m 333 vw(4) 347 vw(5)

367 vw(4) 358 m(17) 489 m 448 450

m(19) vs(73)

385 vw(4) 370 m(21) 500 m 467 s(53) 464 s(37) 419 m(17) 390 m(17) 518 m 484 vs(51) 432 vw(2) 427 m(10) 528 m 494 s(26) 448 m(19) 464 s(37) 536 s 537 mw 450 vs(73) 484 vs(51) 561 s 561 mw 467 s(53) 494 s(26) 571 m 571 w 468 vw(1) 542 s(40) 589 m 542 s(40) 638 w - - 728 s 728 s 756 m 755 w 831 m 832 m 863 w - - 976 vs 973 vs

- - 1075 w (sh) 1136 s 1133 m (sh) 1161 s 1169 ms 1220 s 1219 vs 1247 vs 1242 vs 1264 s - - 1277 s 1276 vs 1299 s 1301 s 1353 m 1353 ms

19

Tab. C. Assignment of experimentally observed vibrational modes in 2a, 2b and 3a.

a) in 2a the vibration ?s(X–P–X) is very strongly coupled with ?s(S–Pap–S)

Additional Information to the X-ray Structures

Tab. D. Fluorine contacts [Å] of the phosphorus-sulfide halogen cations below 3.5 Å (P, the

sum of van der Waals radii for P and F - 3.4 Å), 3.4 Å (S, the sum of van der Waals radii for S

and F - 3.3 Å), 3.5 Å (Br, the sum of van der Waals radii for Br and F – 3.4 Å) and 3.7 Å (I,

the sum of van der Waals radii for I and F – 3.6 Å).

P5S2I2+ P5S2Br2

+ I1–F24 3.309 Br1–F15 3.097 I1–F33 3.496 Br1–F34 3.272 I1–F8 3.585 Br1–F20 3.353 I2–F2 3.339 Br2–F11 3.087 I2–F14 3.537 Br2–F27 3.322 I2–F18 3.609 Br2–F1 3.498 P1– no contact <4.0 P1 no contact <3.9 Å P2–F29 no contact <3.515 P2–F8 3.475 P5–F1 3.253 P5–F10 3.327 P5–F17 3.284 P5–F31 3.364 P5–F30 3.341 P4–F23 3.254 P4–F36 3.280 P4–F10 3.300 P4–F1 3.391 P4–F29 3.517 P4–F31 3.469 P3–F19 3.143 P3–F1 3.232 P3–F35 3.304 P3–F10 3.395 P3–F14 3.454 S2–F23 3.173 S2–F9 3.269 S2–F29 3.391 S1–F18 3.110 S1–F21 3.139 S1–F4 3.235 S1–F26 3.256

2a 2b Assignment 2ab (Cs)

3a Assignment 3a (C1)

- (151) 154 (135) ?s(Pap–PX2–Pbas) 235 (214) ds(Pap–S2) 230 (203) 229 (202) ds(Pap–S2) 375 (358) ?(BrPbas–Pbas) n.o. (278) 290 (269) d (S2–Pap–PX2) 392 (379) ?s(S–Pap–S) 346 (323) 335 (317) ?(S2–Pap–PX2) 409 (390) ?as(Pbas–Sap–Pap) n.o. (432) ?(X2P–Pap) 437 (427) ?s(Pbas–Sap–Pap)

422 (419) 404 (365) 404 (366) ?s(X–P–X) 500 (464) ?as(Pbas–Pbas–Br)

500 (467) 427 (383) ?as(X–P–X) 518 (484) ?as(Br–Pbas–Sap) n.o. (385) 436 (391) ?as(Pbas–S2) 528 (496) ?(Pbas–Sap) 489 (448) 483 (458) ?as(Pap–S2) 589 (542) ?as(Sbas–Pbas–Sap) 489 (450) 442 (423) ?(X2P–Pbas)

n.o. (419) a) 442 (433) ?s(S–Pap–S) n.o. (468) 491 (465) ?s(P3)

20

Fig. I. Solid state packing of 2b (perspective view, right). The anions are represented by AlO 4

polyhedra and all C(CF3)3 groups were omitted for clarity. The cations were drawn with thermal ellipsoids at the 25% probability level. A primitive cubic packing of the ions in 2b - a section of the solid state structure. The [Al(OR)4]– anion is surrounded by 8 P5S2I2

+ cations forming a distorted cubic coordination sphere.

Fig. J. Solid state packing of 2a (perspective view, left). The anions are represented by AlO 4 polyhedra and all C(CF3)3 groups were omitted for clarity. The cations were drawn with thermal ellipsoids at the 25% probability level. Cubic primitive packing of the ions in 2a.

21

Additionally calculated Thermodynamics

All reactions with respect to the finally assigned P5S3X2+ Structure.

Reactions ?H° ?G° ?G°(CH2Cl2)

P4S3 + PBr3 + Ag(CH2Cl2)3+ ? P5S3Br2

+ + 3CH2Cl2 + AgBr 159 85 22

P4S3+ PI3 + Ag(CH2Cl2)3+ ? P5S3I2

+ + 3CH2Cl2 + AgI 115 43 –11

2P5S3Br2+ ? P5S2Br2

+ + P4S4Br+ + 1/6 P6Br6 (+25°C) 2 –5 –12

2P5S3Br2+ ? P5S2Br2

+ + P4S4Br+ + 1/6 P6Br6 (–30°C) 2 –3 –12

2P5S3Br2+ ? P5S2Br2

+ + P4S4Br+ + 1/6 P6Br6 (–80°C) 2 –2 –11

2P5S3I2+ ? P5S2I2+ + P4S4I+ + 1/6 P6I6 (+25°C) 8 1 –10

2P5S3I2+ ? P5S2I2+ + P4S4I+ + 1/6 P6I6 (–30°C) 8 2 –10

2P5S3I2+ ? P5S2I2+ + P4S4I+ + 1/6 P6I6 (–80°C) 8 3 –9

22

Tab. E. Total energy (MP2/TZVPP), zero point energy (BP/SVP), solvation energy and thermal and entropic contributions (BP/SVP) to the free energy at 298K of all calculated

species in [H].

Molecule (symmetry) U (MP2/TZVPP)

ZPE (BP/SVP)

Hsolv(BP86/SVP) COSMO

Thermal+Entropic correc. to G at 298K

P4S3 (C3v) –2556.82829 0.01168 –0.00290 –0.02323 P5S2Br2

+ (Cs) –7644.92783 0.01363 –0.06302 –0.03064 P5S2I2

+ (Cs) –2522.42426 0.01296 –0.06176 –0.03322 (Pbas–S) P5S3Br2

+ (C1) –8042.63516 0.01497 –0.06152 –0.03300 (S–Pap) P5S3Br2

+ (C1) –8042.63035 0.01493 –0.06095 –0.03262 (P–P) P5S3Br2

+ (C1) –8042.65058 0.01518 –0.06283 –0.03181 (P–P) P5S3I2+ (C1) –2920.14678 0.01457 –0.06165 –0.03404

(S–Pap) P5S3I2+ (C1) –2920.12429 0.01428 –0.05991 –0.03490 (Pbas–S) P5S3I2+ (C1) –2920.12694 0.01421 –0.06031 –0.03295

Pap-PBr2P4S3+ -8042.651152 0.0148826 -0.06272901 -0.034972386

S-PBr2P4S3+ -8042.645926 0.014538 -0.062983331 -0.03429442

Pbas-PBr2P4S3+ -8042.651652 0.0149934 -0.061714275 -0.029030661

Pap-PI2P4S3+ -2920.144372 0.0144223 -0.061740973 -0.036389259

S-PI2P4S3+ -2920.135786 0.0139521 -0.062062033 -0.036789183

Pbas-PI2P4S3+ -2920.144757 0.0145225 -0.060702864 -0.036156922

Final: P5S3Br2+ (Iso 7) -8042.656559 0.01527 -0.06257 -0.02901

Final: P5S3I2+ (Iso 7)

PI2+ (C2v) –363.24680 0.00221 –0.07384 –0.02902

PBr2+ (C2v) –5485.74848 0.00264 –0.07953 –0.02701

PI3 (C3v) –374.91413 0.00301 –0.00281 –0.03386 PBr3 (C3v) –8058.68874 0.00368 –0.00188 –0.02972

AgBr (C8 v) –2719.12161 0.00056 –0.01338 –0.02495 AgI (C8 v) –157.86742 0.00047 –0.01270 –0.02580

CH2Cl2 (C2v) –958.61384 0.02794 –0.00404 0.00062 Ag(CH2Cl2)3

+ (C2) –3022.16690 0.08808 –0.06004 0.02628 PI (C8 v) –352.16389 0.00080 –0.00557 –0.02379 P2I2 (C2) –704.45075 0.00332 –0.00202 –0.03175

P4I4 (C2v) –1408.97220 0.00817 –0.00467 –0.04261 P6I6 (D3d) –2113.48344 0.01235 –0.00591 –0.04733

P4S4I+ (C1) –2965.63103 0.01398 –0.06453 –0.02962 P4S4Br+ (C1) –5526.88390 0.01447 –0.06542 –0.02790

P6Br6 (D3d) –17481.00278 0.01430 –0.00334 –0.04552 S8 (D4d) –3181.72527 0.01088 –0.00216 –0.02941 S2 (D8 h) –795.39368 0.00157 –0.00281 –0.01894

a) imaginary frequency at –25 cm–1 b) imaginary frequency at –33 cm–1

23

Table F: Total energies at the MPW1PW91 level, ZPEs, entropic contributions and solvation enthalpies at the BP86/SVP level. Values in red are non standard temperatures (-30°C and -78°C).

All with 6-311G(2df) Basis U [H] mpw1pw91

ZPE [H] aoforce

Hsolv(BP/SVP) 8.93 (25)

/11.46 (-30)/ 14.95 (-78)

Entrop- freeh

BP/SVP

P7S6Br2+ -9927.67508 0.02351 -0.05855 -0.03242 (+25°C) P4S3 -2560.34103 0.01168 -0.00309 -0.02246 (-30°C) P4S3 -2559.34103 0.01168 -0.00323 -0.01468 (-78°C) P4S3 -2558.34103 0.01168 -0.00335 -0.00836

(+25°C) P5S2Br2+ -7651.86304 0.01363 -0.06302 -0.02821 (-30°C) P5S2Br2+ -7651.86304 0.01363 -0.06517 -0.01834 (-80°C) P5S2Br2+ -7651.86304 0.01363 -0.06731 -0.01038

(+25°C) iso1 P-S P5S3Br2+ -8050.08701 0.01496 -0.06152 -0.03037 (-30°C) iso1 P-S P5S3Br2+ -8050.08701 0.01496 -0.06316 -0.01956 (-80°C) iso1 P-S P5S3Br2+ -8050.08701 0.01496 -0.06525 -0.01086

iso2 S-P P5S3Br2+ 0.01493 -0.06095 -0.03262 iso3 P-P P5S3Br2+ 0.01518 -0.06283 -0.02903

(+25°C) iso4 Pbas(PX2+) P5S3Br2+ -8050.10624 0.01457 -0.06165 -0.03243 (-30°C) iso4 Pbas(PX2+) P5S3Br2+ -8050.10624 0.01457 -0.06444 -0.02124 (-78°C) iso4 Pbas(PX2+) P5S3Br2+ -8050.10624 0.01457 -0.06662 -0.01221

iso5 S(PX2+) P5S3Br2+ -8050.09527 0.01428 -0.05991 -0.03490 iso6 Papi(PX2+) P5S3Br2+ -8050.10341 0.01421 -0.06031 -0.03295

(+25°C) iso7 cis 4-ring pbr-pbr+ -8050.11123 0.01527 -0.06257 -0.02901 (-30°C) iso7 cis 4-ring pbr-pbr+ -8050.11123 0.01527 -0.06514 -0.01843 (-78°C) iso7 cis 4-ring pbr-pbr+ -8050.11123 0.01527 -0.06731 -0.00994

iso8 trans 4-ring pbr-pbr+ -8050.10502 0.01529 -0.06348 -0.02859 (+25°C) PBr2+ -5489.69697 0.00236 -0.07953 -0.02701 (-30°C) PBr2+ -5489.69697 0.00236 -0.08506 -0.02085 (-80°C) PBr2+ -5489.69697 0.00236 -0.08790 -0.01560

PBr3 -8064.36758 0.00368 -0.00188 -0.02972 AgBr -2721.36305 0.00056 -0.01338 -0.02495 Ag+ -146.71656 0.00000 -0.09216 -0.01661

Ag(CH2Cl2)3+ -3026.14065 0.08718 -0.06004 0.02628 CH2Cl2 -959.77368 0.02837 -0.00404 -0.00083

(+25°C) P2Br2 -5831.40427 0.00379 -0.00140 -0.02948 (-30°C) P2Br2 -5831.40427 0.00379 -0.00153 -0.02225 (-80°C) P2Br2 -5831.40427 0.00379 -0.00160 -0.01621

(+25°C) P4S4Br+ -5532.63554 0.01447 -0.06542 -0.02544 (-30°C) P4S4Br+ -5532.63554 0.01447 -0.06767 -0.01602 (-80°C) P4S4Br+ -5532.63554 0.01447 -0.06991 -0.00844

(+25°C) P6Br6 -17494.31246 0.01430 -0.00402 -0.04218 (-30°C) P6Br6 -17494.31246 0.01430 -0.00421 -0.02836 (-80°C) P6Br6 -17494.31246 0.01430 -0.00437 -0.01723

S8 -3185.86549 0.01088 -0.00216 -0.02941 S2 -796.43053 0.00157 -0.00281 -0.01894

24

P1

P2

P3

P4P5

S1

S2

Br1

Br2

2.2532.226

2.1782.136

P5S2Br2+ (Cs)

2.085

2.2272.155

P1

P2

P3

P4P5

S1

S2

Br1

Br2

2.2532.226

2.1782.136

P5S2Br2+ (Cs)

2.085

2.2272.155P1

P2

P3

P4P5

S1

S2 I1

I2

2.084

2.233

2.2292.251

2.133

2.182

2.376

P5S2I2+ (Cs)

P1

P2

P3

P4P5

S1

S2 I1

I2

2.084

2.233

2.2292.251

2.133

2.182

2.376

P5S2I2+ (Cs)

ß-P4S3I2(C2)ß-P4S3I2(C2)4 3 2 24 3 2 2

2.246

2.091

2.103P

SS

S

P

P

P

P4S4I+ (C1)

2.246

2.091

2.103P

SS

S

P

P

P

P4S4I+ (C1)

P4S4Br+ (C1)

2.049

2.150

2.0582.110 2.139

2.106

2.0602.113

2.193

2.159

2.304

S

Br

S

P

SS

P

P

P

P4S4Br+ (C1)

2.049

2.150

2.0582.110 2.139

2.106

2.0602.113

2.193

2.159

2.304

S

Br

S

P

SS

P

P

P

P4S4I+ (C1)

2.305

2.190

2.058

2.062

2.3652.224

2.154

2.059

2.1392.109

I

S

S

S

P

P

P

P

P4S4I+ (C1)

2.305

2.190

2.058

2.062

2.3652.224

2.154

2.059

2.1392.109

I

S

S

S

P

P

P

P

Figure K. Optimized structures of P4S3, [P5S2X2]+ and [P4S4X]+ (X = Br, I) at the

MP2/TZVPP level. All species are true minima with no imaginary frequencies, according to

the frequency calculation of the DFT-optimized geometries at the BP86/SV(P) level.

P2Br2 (C2h)P

P

Br

Br

2.050

2.233

96.6°

P2Br2 (C2h)P

P

Br

Br

P2Br2 (C2h)P

P

Br

Br

2.050

2.233

96.6°

P2I2 (C2h)

P

P I

I

2.050

2.445

96.5°

P2I2 (C2h)

P

P I

I

P2I2 (C2h)

P

P I

I

2.050

2.445

96.5°

P6I6 (D3d)

2.244

2.447

P

P

P

PP

P

I

II

I

I

I

92.3° 94.8°

P6I6 (D3d)P6I6 (D3d)

2.244

2.447

P

P

P

PP

P

I

II

I

I

I

92.3° 94.8°

P6Br6 (D3d)

2.238 2.246

P

Br

Br

Br

Br

Br

Br P

PP P

P

91.3°

96.0°

P6Br6 (D3d)

2.238 2.246

P

Br

Br

Br

Br

Br

Br P

PP P

P

91.3°

96.0°

Figure L. Optimized structures of P2X2 (C2h) and P6X6 (D3d) (X = Br, I) at the MP2/TZVPP

level. All species are true minima with no imaginary frequencies, according to the frequency

calculation of the DFT-optimized geometries at the BP86/SV(P) level.

25

Details to the quantum chemical calculations Deposited data on the calculated structures: The following pages contain total energies, xyz-coordinates, thermal and entropic contributions, zero point energies and vibrational frequencies of the calculated compounds at the given level of theory.

• Ag(P4S3)(PBr3)+ Nine isomers at the BP86/SVP level • Ag(CH2Cl2)(PBr3)+ Three isomers at the BP86/SVP level • P5S3X2

+ Seven isomers at the MP2/TZVPP and MPW1PW91 levels • P5S2X2

+ at the MP2/TZVPP level • P4S4X+ at the MP2/TZVPP level • Small particles necessary for the thermodynamics. • The calculated chemical shifts and coupling constants at the MPW1PW91 level

Ag(P4S3)(PBr3)

+ Nine isomers at the BP86/SVP level ~/psx-nmr/agp4s3px3/br/api_px3> (BP86/SVP)

cycle = 28 SCF energy = -10770.2857734900 |dE/dxyz| = 0.000499 HOMO-LUMO Separation HOMO: 123. 123 a -0.36460519 H = -9.92142 eV LUMO: 124. 124 a -0.27512857 H = -7.48663 eV Gap : +0.08947661 H = +2.43478 eV Number of MOs= 264, Electrons= 246.00, Symmetry: c1

26

P -0.0164597 -2.3629136 0.0087240 S 1.5461734 -3.2665178 1.1351217 P 0.1585880 -5.3242661 -1.3344849 S -1.7613230 -3.3004932 0.7846760 P 1.0961407 -5.3273216 0.7752863 P -1.2038117 -5.3492601 0.5312079 S 0.1948876 -3.2646372 -1.9073465 Ag -0.0211999 0.0480527 0.0029698 P -0.0000748 2.4844703 -0.0010930 Br 0.3573300 3.3458116 -2.0144892 Br 1.5777442 3.3308181 1.3093455 Br -1.9116531 3.3585417 0.7040302 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 8.04 0.00205 YES YES 8 a 13.39 0.05072 YES YES 9 a 15.04 0.04709 YES YES 10 a 42.73 0.02392 YES YES 11 a 43.21 0.02141 YES YES 12 a 67.61 0.31155 YES YES 13 a 76.57 0.01868 YES YES 14 a 76.63 0.01798 YES YES 15 a 109.61 0.04224 YES YES 16 a 111.44 0.02932 YES YES 17 a 139.80 5.13700 YES YES 18 a 177.53 0.00045 YES YES 19 a 187.69 1.90941 YES YES 20 a 214.82 3.05806 YES YES 21 a 215.34 3.04999 YES YES 22 a 276.33 0.32334 YES YES 23 a 276.51 0.31605 YES YES 24 a 315.85 0.01143 YES YES 25 a 317.89 0.01119 YES YES 26 a 367.85 5.71207 YES YES 27 a 395.93 22.07616 YES YES 28 a 412.61 72.99136 YES YES 29 a 414.47 47.43200 YES YES 30 a 415.49 61.72491 YES YES 31 a 418.92 24.43477 YES YES 32 a 419.52 18.59283 YES YES 33 a 429.27 2.72992 YES YES 34 a 464.52 0.34777 YES YES 35 a 476.08 6.31091 YES YES 36 a 476.85 6.16580 YES YES ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 44.13 kJ/mol

27

T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 20.20 16.93 22.73 -104.25 93.56 0.67174 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.2392679 0.2475822

~/psx-nmr/agp4s3px3/br/api_xpx2> (BP86/SVP)

cycle = 73 SCF energy = -10770.2842915300 |dE/dxyz| = 0.000442 HOMO-LUMO Separation HOMO: 123. 123 a -0.36460519 H = -9.92142 eV LUMO: 124. 124 a -0.27512857 H = -7.48663 eV Gap : +0.08947661 H = +2.43478 eV Number of MOs= 264, Electrons= 246.00, Symmetry: c1 P -2.7955428 0.1527347 0.3031862 S -3.2112310 -0.3909762 -1.7118694 P -5.8431559 1.2425933 -0.0760312 S -3.9170263 -1.2726947 1.4151847 P -5.3500609 -0.3762429 -1.6488624 P -5.8404114 -0.9882903 0.5239534 S -3.9214725 1.9403065 0.5522716 Ag -0.5124302 0.3305061 0.9447463 P 3.2042535 0.7282011 -0.1507128 Br 1.8481324 0.5827528 1.9002004 Br 2.3066601 -0.9359541 -1.3542620 Br 5.1052900 -0.1069860 0.6079375 $vibrational spectrum # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 a -13.01 0.00000 YES YES 2 0.00 0.00000 - - 3 0.00 0.00000 - -

28

4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 0.00 0.77458 - - 8 a 2.19 0.02281 YES YES 9 a 9.59 0.01755 YES YES 10 a 20.35 0.06907 YES YES 11 a 28.42 0.08495 YES YES 12 a 64.89 0.01177 YES YES 13 a 68.13 0.03221 YES YES 14 a 72.75 0.09341 YES YES 15 a 96.97 1.80755 YES YES 16 a 115.99 0.05049 YES YES 17 a 135.77 2.17460 YES YES 18 a 178.14 0.00043 YES YES 19 a 187.39 20.21819 YES YES 20 a 214.69 3.27727 YES YES 21 a 215.08 3.15693 YES YES 22 a 270.62 84.02605 YES YES 23 a 276.61 0.15597 YES YES 24 a 276.79 0.26453 YES YES 25 a 316.73 0.03258 YES YES 26 a 317.04 0.01735 YES YES 27 a 369.42 2.47944 YES YES 28 a 382.33 41.30540 YES YES 29 a 396.86 25.64778 YES YES 30 a 404.12 102.92895 YES YES 31 a 418.46 6.03956 YES YES 32 a 419.66 6.46947 YES YES 33 a 429.88 0.54650 YES YES 34 a 466.85 2.18034 YES YES 35 a 476.20 5.20846 YES YES 36 a 476.63 5.30468 YES YES ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 imaginary frequency not included in vib. partition sum zero point vibrational energy ----------------------------- zpe= 42.52 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 20.20 16.88 23.21 -106.93 90.48 0.67045 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.2326091 0.2409234

29

/psx-nmr/agp4s3px3/br/api_x2px> (BP86/SVP)

cycle = 31 SCF energy = -10770.2848153700 |dE/dxyz| = 0.000984 HOMO-LUMO Separation HOMO: 123. 123 a -0.35845599 H = -9.75409 eV LUMO: 124. 124 a -0.27808378 H = -7.56705 eV Gap : +0.08037221 H = +2.18704 eV Number of MOs= 264, Electrons= 246.00, Symmetry: c1 P -2.3964443 0.0484143 0.1715008 S -3.1366581 -1.0674369 -1.4819915 P -5.2119166 1.5644972 -0.4766358 S -3.6370930 -0.6098440 1.7710461 P -5.2134017 -0.5705914 -1.3590473 P -5.5601660 -0.2552111 0.9024021 S -3.1347926 2.0063540 -0.2171301 P 3.5670601 -0.8252253 0.1209845 Br 2.2114708 -0.0953932 1.9338967 Br 4.9956886 0.8388762 -0.1219006 Br 2.0157875 -0.4520914 -1.5534020 Ag -0.0393417 -0.0953347 0.4802868 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 9.73 0.00838 YES YES 8 a 10.79 0.02641 YES YES 9 a 14.48 0.07933 YES YES 10 a 29.89 0.03779 YES YES 11 a 54.85 1.54094 YES YES 12 a 58.26 1.05222 YES YES 13 a 68.94 0.06939 YES YES 14 a 71.32 0.02141 YES YES

30

15 a 95.90 0.27653 YES YES 16 a 117.15 0.10492 YES YES 17 a 142.86 4.10664 YES YES 18 a 174.08 15.78681 YES YES 19 a 177.84 0.00126 YES YES 20 a 214.67 3.24279 YES YES 21 a 214.81 3.12512 YES YES 22 a 276.53 0.36329 YES YES 23 a 277.04 0.41961 YES YES 24 a 302.31 54.43059 YES YES 25 a 316.64 0.32378 YES YES 26 a 317.07 0.22935 YES YES 27 a 344.04 75.85705 YES YES 28 a 368.38 2.35530 YES YES 29 a 396.20 23.39327 YES YES 30 a 409.04 98.32763 YES YES 31 a 417.57 6.57222 YES YES 32 a 418.71 5.72372 YES YES 33 a 429.12 0.53678 YES YES 34 a 465.28 2.73819 YES YES 35 a 474.81 5.37822 YES YES 36 a 475.42 4.88432 YES YES ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 42.73 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 20.20 16.79 23.46 -107.12 92.90 0.67922 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.2410558 0.2493701

31

/psx-nmr/agp4s3px3/br/s_px3> (BP86/SVP)

cycle = 57 SCF energy = -10770.2873156200 |dE/dxyz| = 0.000349 HOMO-LUMO Separation HOMO: 123. 123 a -0.37994551 H = -10.33885 eV LUMO: 124. 124 a -0.27230958 H = -7.40992 eV Gap : +0.10763592 H = +2.92892 eV P -3.1093774 0.0241730 1.7364744 S -2.3396004 1.6053699 0.4162758 P -5.1279847 0.0196815 -0.9493544 S -2.3939955 -1.6243050 0.4524450 P -3.2204917 1.1435383 -1.5084358 P -3.2543184 -1.1705421 -1.4881303 S -5.1587007 0.0425125 1.1902240 P 2.1705527 -0.0083046 -0.0008417 Br 2.8092217 0.5635424 -2.0535274 Br 3.1153171 1.4851170 1.3478833 Br 3.2184945 -1.9205769 0.4277360 Ag -0.2314122 -0.1043444 0.2285192 Number of MOs= 264, Electrons= 246.00, Symmetry: c1 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 7.50 0.00492 YES YES 8 a 10.85 0.05457 YES YES 9 a 17.62 0.04249 YES YES 10 a 40.39 0.00618 YES YES 11 a 52.18 0.18411 YES YES 12 a 63.73 0.02851 YES YES 13 a 67.46 0.08701 YES YES 14 a 75.20 0.19031 YES YES 15 a 109.74 0.04925 YES YES 16 a 110.87 0.04971 YES YES

32

17 a 132.40 6.00724 YES YES 18 a 185.42 0.75343 YES YES 19 a 186.47 0.48943 YES YES 20 a 216.19 1.23269 YES YES 21 a 256.12 24.89914 YES YES 22 a 273.89 0.49623 YES YES 23 a 280.25 0.48254 YES YES 24 a 310.85 0.19474 YES YES 25 a 325.12 0.55778 YES YES 26 a 332.32 0.30740 YES YES 27 a 349.82 8.48089 YES YES 28 a 356.04 8.84242 YES YES 29 a 397.83 31.51814 YES YES 30 a 410.91 80.65983 YES YES 31 a 412.79 82.12550 YES YES 32 a 415.39 28.16656 YES YES 33 a 417.71 29.73775 YES YES 34 a 427.73 0.53724 YES YES 35 a 438.86 2.38809 YES YES 36 a 462.24 3.42387 YES YES ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 42.73 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 20.20 16.75 23.04 -105.97 92.72 0.67471

33

/psx-nmr/agp4s3px3/br/s_xpx2> (BP86/SVP)

Unsymmetrical Ag-environment! 1 Ag-S and Ag-P short and 1 Ag-S and Ag-P

longer than 324.7 pm!

cycle = 62 SCF energy = -10770.2838925900 |dE/dxyz| = 0.000444 HOMO-LUMO Separation HOMO: 123. 123 a -0.37133762 H = -10.10462 eV LUMO: 124. 124 a -0.27650931 H = -7.52421 eV Gap : +0.09482830 H = +2.58041 eV Number of MOs= 264, Electrons= 246.00, Symmetry: c1 P -3.6830865 1.9903394 3.9227507 S -2.6131016 3.2275086 2.3964620 P -4.4458603 0.6807523 0.9153525 S -2.4213644 0.2487552 3.7241498 P -2.5360626 1.9151805 0.6583133 P -2.4496043 -0.1793454 1.6189932 S -5.3377194 1.4516944 2.7043746 P 3.3979310 3.7443536 3.1087434 Br 3.9982407 2.3057993 1.5295409 Br 1.8573106 5.0355267 2.0924974 Br 1.9173381 2.3852781 4.4609441 Ag -0.3884066 2.7539676 3.3588930 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 7.63 0.00533 YES YES 8 a 13.59 0.13674 YES YES 9 a 16.46 1.35571 YES YES 10 a 21.61 0.71345 YES YES

34

11 a 22.52 0.15232 YES YES 12 a 26.79 1.48175 YES YES 13 a 59.14 0.06289 YES YES 14 a 81.21 0.45726 YES YES 15 a 96.11 1.14313 YES YES 16 a 112.71 0.29127 YES YES 17 a 145.01 3.07869 YES YES 18 a 170.11 4.58636 YES YES 19 a 186.92 0.32940 YES YES 20 a 213.30 3.23136 YES YES 21 a 269.26 5.62436 YES YES 22 a 277.19 64.83399 YES YES 23 a 281.73 0.16216 YES YES 24 a 289.72 6.65244 YES YES 25 a 312.82 3.78141 YES YES 26 a 318.76 1.67528 YES YES 27 a 331.25 2.94935 YES YES 28 a 338.29 6.95934 YES YES 29 a 376.38 18.86806 YES YES 30 a 378.61 36.94899 YES YES 31 a 399.33 27.96418 YES YES 32 a 402.02 70.74506 YES YES 33 a 415.04 0.57129 YES YES 34 a 431.67 1.52983 YES YES 35 a 444.92 1.19158 YES YES 36 a 460.17 3.84367 YES YES No Entropy due to Nimag=1

35

/psx-nmr/agp4s3px3/br/s_x2px> (BP86/SVP)

cycle = 146 SCF energy = -10770.2837049400 |dE/dxyz| = 0.000531 HOMO-LUMO Separation HOMO: 123. 123 a -0.36795576 H = -10.01259 eV LUMO: 124. 124 a -0.26747056 H = -7.27825 eV Gap : +0.10048520 H = +2.73434 eV Number of MOs= 264, Electrons= 246.00, Symmetry: c1 P 2.9208805 1.4185940 -1.0998824 S 2.4640257 1.2595430 1.0444222 P 5.1821518 -0.7311043 0.1488040 S 2.1676040 -0.5925484 -1.5955334 P 3.4639027 -0.5603128 1.6458433 P 3.2489260 -1.8873172 -0.2353890 S 5.0059656 1.0233781 -1.0658875 Ag 0.1854498 0.1092920 0.0470001 P -3.4923581 -0.1101999 0.8431930 Br -2.0654572 1.7213715 0.6809269 Br -1.8665034 -1.7543928 0.4868282 Br -4.5746686 -0.0678170 -1.0872631 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 7.85 0.01594 YES YES 8 a 11.91 0.04883 YES YES 9 a 12.59 0.00695 YES YES 10 a 21.15 0.15729 YES YES 11 a 30.06 0.12632 YES YES 12 a 52.22 0.05759 YES YES 13 a 63.12 0.75765 YES YES 14 a 72.02 0.30173 YES YES 15 a 95.64 0.11015 YES YES 16 a 108.80 0.80251 YES YES 17 a 138.24 16.34344 YES YES 18 a 152.63 2.29968 YES YES 19 a 184.57 0.17799 YES YES

36

20 a 213.76 1.43265 YES YES 21 a 251.44 20.09273 YES YES 22 a 274.65 0.45952 YES YES 23 a 280.77 0.59571 YES YES 24 a 310.10 18.96050 YES YES 25 a 312.21 24.97665 YES YES 26 a 325.10 0.53164 YES YES 27 a 333.23 0.28913 YES YES 28 a 340.05 72.14986 YES YES 29 a 351.88 10.32672 YES YES 30 a 356.57 9.47833 YES YES 31 a 399.15 31.74274 YES YES 32 a 405.01 79.55745 YES YES 33 a 416.49 0.25243 YES YES 34 a 430.37 0.24147 YES YES 35 a 438.86 2.86077 YES YES 36 a 460.62 4.13489 YES YES ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 40.98 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 20.20 16.64 25.01 -112.32 92.04 0.69377 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.2432840 0.2515983

37

/psx-nmr/agp4s3px3/br/bas_px3> (BP86/SVP)

cycle = 37 SCF energy = -10770.2871556600 |dE/dxyz| = 0.000620 HOMO-LUMO Separation HOMO: 123. 123 a -0.36944286 H = -10.05306 eV LUMO: 124. 124 a -0.27365068 H = -7.44642 eV Gap : +0.09579219 H = +2.60664 eV Number of MOs= 264, Electrons= 246.00, Symmetry: c1 P -5.2973203 -0.0067787 1.2546674 S -5.2420290 -1.6619123 -0.1348911 P -2.3118562 0.0083446 -0.0571485 S -5.2568913 1.6503266 -0.1370915 P -3.6710294 -1.1647508 -1.4665166 P -3.6837665 1.1641874 -1.4698721 S -3.2084102 0.0055251 1.8500790 Ag 0.0988354 0.0026046 -0.0066636 P 2.5302118 -0.0009952 0.0137173 Br 3.3943703 -1.7976090 0.9838097 Br 3.4003313 0.0587438 -2.0263481 Br 3.3915263 1.7377784 1.0870046 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 11.25 0.00972 YES YES 8 a 15.52 0.08881 YES YES 9 a 18.52 0.05234 YES YES 10 a 41.14 0.01402 YES YES 11 a 44.39 0.03067 YES YES 12 a 67.15 0.34153 YES YES 13 a 71.56 0.00748 YES YES 14 a 76.47 0.09845 YES YES 15 a 110.95 0.06931 YES YES 16 a 112.12 0.04263 YES YES 17 a 137.96 4.71249 YES YES 18 a 184.96 0.00531 YES YES

38

19 a 188.80 1.67083 YES YES 20 a 209.87 3.22674 YES YES 21 a 214.18 2.97653 YES YES 22 a 279.03 0.00389 YES YES 23 a 295.36 3.26599 YES YES 24 a 336.75 1.39423 YES YES 25 a 338.60 0.47275 YES YES 26 a 344.58 4.11203 YES YES 27 a 370.57 6.93970 YES YES 28 a 378.43 9.86746 YES YES 29 a 380.98 6.67072 YES YES 30 a 416.91 69.34010 YES YES 31 a 418.35 70.93024 YES YES 32 a 419.93 86.39121 YES YES 33 a 450.21 5.11121 YES YES 34 a 455.06 3.40144 YES YES 35 a 469.29 2.24986 YES YES 36 a 494.81 1.81911 YES YES ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 43.98 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 20.20 16.97 22.11 -102.97 93.44 0.66706 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.2395737 0.2478880

39

~/psx-nmr/agp4s3px3/br/bas_xpx2> (BP86/SVP)

cycle = 51 SCF energy = -10770.2852796200 |dE/dxyz| = 0.000535 HOMO-LUMO Separation HOMO: 123. 123 a -0.36565499 H = -9.94998 eV LUMO: 124. 124 a -0.27811773 H = -7.56797 eV Gap : +0.08753725 H = +2.38201 eV Number of MOs= 264, Electrons= 246.00, Symmetry: c1 P -5.7560789 -0.3340801 0.9020602 S -5.6938294 1.2783408 -0.5407496 P -3.5800856 -1.3421206 -1.4756267 S -3.8096713 -0.0455196 1.8172947 P -3.8739770 0.9679588 -1.5775882 P -2.6202195 0.0282131 0.0793896 S -5.2734732 -2.0036570 -0.3878460 Ag -0.3076232 0.3904902 0.5142019 P 3.3450221 -0.8301664 -0.2423544 Br 2.1339879 0.8877102 1.0659606 Br 3.7973795 0.3009430 -2.1013954 Br 5.2527370 -0.8211053 0.8816958 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 4.98 0.01860 YES YES 8 a 8.99 0.01229 YES YES 9 a 12.59 0.04688 YES YES 10 a 21.71 0.09965 YES YES 11 a 30.28 0.00514 YES YES 12 a 63.62 0.04509 YES YES 13 a 70.64 0.12220 YES YES 14 a 73.13 0.16618 YES YES 15 a 92.69 0.89615 YES YES 16 a 108.66 1.16490 YES YES 17 a 138.24 1.41676 YES YES 18 a 184.06 30.85815 YES YES 19 a 185.76 1.54665 YES YES 20 a 210.50 3.34020 YES YES

40

21 a 213.68 2.48049 YES YES 22 a 268.14 92.93372 YES YES 23 a 279.25 0.00216 YES YES 24 a 294.96 1.87155 YES YES 25 a 337.30 1.37124 YES YES 26 a 339.42 0.45616 YES YES 27 a 346.70 2.58336 YES YES 28 a 371.21 7.54134 YES YES 29 a 378.90 10.43688 YES YES 30 a 379.66 6.75446 YES YES 31 a 394.33 54.14454 YES YES 32 a 407.97 97.62038 YES YES 33 a 451.22 5.09354 YES YES 34 a 458.39 3.76697 YES YES 35 a 470.07 2.25597 YES YES 36 a 496.30 1.27519 YES YES ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 42.43 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 20.20 17.04 25.22 -112.41 92.85 0.69678 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.2412116 0.2495259

41

~/psx-nmr/agp4s3px3/br/bas_x2px> (BP86/SVP)

cycle = 115 SCF energy = -10770.2858282600 |dE/dxyz| = 0.000594 HOMO-LUMO Separation HOMO: 123. 123 a -0.36211811 H = -9.85374 eV LUMO: 124. 124 a -0.27662277 H = -7.52729 eV Gap : +0.08549534 H = +2.32645 eV Number of MOs= 264, Electrons= 246.00, Symmetry: c1 P -5.0561828 -0.8608354 -1.3133766 S -5.2282523 -1.5470330 0.7302031 P -3.8134497 1.6424132 0.5769616 S -2.9053294 -1.0396216 -1.5485070 P -3.8467809 -0.3431012 1.7939992 P -2.2771432 0.0027757 0.1733214 S -5.1809032 1.2753928 -0.9984495 P 3.7108346 0.8557532 -0.0759737 Br 5.0800453 -0.8483686 -0.3822169 Br 2.0978020 0.5321875 -1.6929176 Br 2.4068412 0.1536385 1.7886349 Ag 0.0971683 0.1377558 0.4206327 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 9.04 0.09054 YES YES 8 a 11.81 0.04436 YES YES 9 a 13.22 0.05475 YES YES 10 a 27.04 0.08267 YES YES 11 a 46.82 1.60375 YES YES 12 a 54.22 1.01743 YES YES 13 a 64.42 0.20877 YES YES 14 a 68.04 0.04028 YES YES 15 a 95.26 0.24117 YES YES 16 a 113.91 0.07133 YES YES 17 a 142.52 5.29063 YES YES 18 a 164.76 13.48026 YES YES 19 a 185.31 0.01259 YES YES 20 a 210.03 3.37263 YES YES 21 a 213.85 2.83840 YES YES

42

22 a 279.59 0.00217 YES YES 23 a 294.60 3.07413 YES YES 24 a 300.32 55.66684 YES YES 25 a 337.58 0.68902 YES YES 26 a 338.52 1.83623 YES YES 27 a 345.25 10.65292 YES YES 28 a 348.95 66.58639 YES YES 29 a 371.58 8.08184 YES YES 30 a 378.61 9.70247 YES YES 31 a 381.00 6.40577 YES YES 32 a 410.23 101.97414 YES YES 33 a 450.82 5.07604 YES YES 34 a 455.68 3.32518 YES YES 35 a 469.62 2.33048 YES YES 36 a 494.03 0.92126 YES YES ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 42.33 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 20.20 16.84 23.99 -108.95 92.75 0.68480 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.2414799 0.2497942

43

Ag(CH2Cl2)(PBr3)+ Three isomers at the BP86/SVP level

/psx-nmr/ag-addukte/agp4s3px3/br/ ch2cl2agpbr3/bp> (BP86/SVP) cycle = 22 SCF energy = -9170.1124306410 |dE/dxyz| = 0.000843 Ag -1.4009078 -0.0021272 0.0076358 C -4.6976200 0.0179899 -0.0187522 Cl -3.6472860 1.4840243 0.0061409 Cl -3.6816926 -1.4709425 -0.0001819 H -5.2911237 0.0282595 -0.9520737 H -5.3295103 0.0242270 0.8890751 P 0.9989174 -0.0000314 0.0007353 Br 1.8542965 -1.2417809 -1.6259751 Br 1.8714966 2.0225809 -0.2672622 Br 1.8698099 -0.7870864 1.8836142 $vibrational spectrum # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 18.43 0.01023 YES YES 8 a 19.61 0.03551 YES YES 9 a 27.50 0.49112 YES YES 10 a 55.11 0.59365 YES YES 11 a 56.01 4.46731 YES YES 12 a 69.14 2.58928 YES YES 13 a 83.42 0.31740 YES YES 14 a 87.47 0.70506 YES YES 15 a 108.63 0.05338 YES YES 16 a 110.97 0.08749 YES YES 17 a 151.57 9.14032 YES YES 18 a 193.30 5.35402 YES YES 19 a 313.55 4.75616 YES YES 20 a 410.79 86.73753 YES YES 21 a 414.40 79.38559 YES YES 22 a 419.21 44.73492 YES YES 23 a 674.01 28.63554 YES YES 24 a 678.77 65.69088 YES YES 25 a 879.42 1.06767 YES YES 26 a 1102.09 0.00069 YES YES 27 a 1232.86 6.22249 YES YES 28 a 1402.54 0.26460 YES YES 29 a 3042.38 3.52629 YES YES 30 a 3137.67 12.12067 YES YES

44

/psx-nmr/ag-addukte/agp4s3px3/br/ ch2cl2agbr2pbr> (BP86/SVP) cycle = 38 SCF energy = -9170.1106877080 |dE/dxyz| = 0.000426 C -4.6410754 -0.2014204 -0.5117635 Cl -3.8796078 -0.0469843 1.1143886 Cl -3.3953062 -0.1158509 -1.8117263 Ag -1.3866066 0.1345120 0.0152154 Br 0.6630098 -1.7362791 0.4072535 P 2.1587491 -0.0177935 0.9434270 Br 0.7946127 1.7905199 0.3012133 Br 3.6348726 -0.1195329 -0.6930080 H -5.3427965 0.6420006 -0.6478958 H -5.1390808 -1.1866317 -0.5709125 $vibrational spectrum # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 9.36 0.38775 YES YES 8 a 12.83 0.29838 YES YES 9 a 19.40 0.48484 YES YES 10 a 22.21 0.07478 YES YES 11 a 48.82 6.81385 YES YES 12 a 60.33 0.29340 YES YES 13 a 71.00 1.41556 YES YES 14 a 82.26 0.78991 YES YES 15 a 94.53 0.37276 YES YES 16 a 122.28 0.15227 YES YES 17 a 142.06 5.95093 YES YES 18 a 162.61 17.98544 YES YES 19 a 307.95 52.59264 YES YES 20 a 309.36 5.88996 YES YES 21 a 332.61 59.87529 YES YES 22 a 410.69 88.25745 YES YES 23 a 673.79 25.50826 YES YES 24 a 677.78 76.16888 YES YES 25 a 878.27 1.09068 YES YES 26 a 1104.76 0.00184 YES YES 27 a 1231.68 8.39867 YES YES 28 a 1401.81 0.42964 YES YES 29 a 3045.48 2.28890 YES YES 30 a 3141.12 10.43438 YES YES

45

/psx-nmr/ag-addukte/agp4s3px3/br/ ch2cl2agbrpbr2> (BP86/SVP) cycle = 28 SCF energy = -9170.1083773290 |dE/dxyz| = 0.000588 C -5.0873826 0.3818050 -0.5352049 Cl -3.7896848 1.6149350 -0.2213005 Cl -4.3807943 -1.2601332 -0.6057611 Ag -1.9044223 -0.1591482 0.1753072 Br 0.4016732 -0.9962918 0.8503824 P 1.8756202 0.0791612 -0.8270643 Br 3.7139335 -1.0920045 -0.4438894 Br 2.2610707 2.0443395 0.1400628 H -5.5488392 0.6215012 -1.5112671 H -5.8063229 0.4333207 0.3033476 $vibrational spectrum # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 a -8.02 0.00000 YES YES 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 0.00 1.83923 - - 8 a 6.58 0.27516 YES YES 9 a 16.83 0.23540 YES YES 10 a 24.33 0.46378 YES YES 11 a 45.76 1.65186 YES YES 12 a 61.33 5.97350 YES YES 13 a 71.45 2.28438 YES YES 14 a 76.65 0.64890 YES YES 15 a 94.21 0.66791 YES YES 16 a 129.26 0.08837 YES YES 17 a 142.17 1.72449 YES YES 18 a 197.55 31.05082 YES YES 19 a 268.87 74.52248 YES YES 20 a 312.61 2.89702 YES YES 21 a 392.47 50.16182 YES YES 22 a 408.47 91.76988 YES YES 23 a 650.22 53.55204 YES YES 24 a 698.96 46.38037 YES YES 25 a 879.60 1.19581 YES YES 26 a 1102.20 0.04014 YES YES 27 a 1230.75 8.00546 YES YES 28 a 1402.36 0.32815 YES YES 29 a 3043.63 2.98586 YES YES 30 a 3139.46 11.33131 YES YES

46

P5S3X2+ Seven isomers at the MP2/TZVPP and MPW1PW91

levels cis-P5S3Br2

+ (C1) (MP2/TZVPP)

cycle = 8 MP2 energy = -8042.6565591906 |dE/dxyz| = 0.000227 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P 0.1488478 0.1843012 0.7236116 P -0.6019747 -1.6409558 -0.2973282 P -0.7914678 -0.1151864 -2.0138241 S -1.4474341 1.2742478 1.4671989 S -2.5043053 -1.6701539 0.5139866 P -3.0875286 0.3796419 0.4085489 S -2.6418642 0.8107373 -1.6065738 P 0.8047989 1.2403547 -1.0855436 Br 2.4365185 -0.1725368 -1.6075253 Br 1.5764456 -0.0125827 2.3349742 Thermodynamics: BP86/SVP cycle = 9 SCF energy = -8048.9728066570 |dE/dxyz| = 0.000527 your wishes are : panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 40.09 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.63 15.68 11.58 -76.16 77.61 0.52406 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1925159 0.2008302 HOMO-LUMO Separation HOMO: 96. 96 a -0.26719839 H = -7.27084 eV LUMO: 97. 97 a -0.17539591 H = -4.77277 eV Gap : +0.09180248 H = +2.49807 eV

47

Number of MOs= 208, Electrons= 192.00, Symmetry: c1 $vibrational spectrum # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 37.75 0.18934 YES YES 8 a 51.15 0.45764 YES YES 9 a 68.49 0.55217 YES YES 10 a 100.36 0.28371 YES YES 11 a 122.42 1.28277 YES YES 12 a 136.89 0.47519 YES YES 13 a 159.25 0.70363 YES YES 14 a 189.28 4.49205 YES YES 15 a 216.13 3.42314 YES YES 16 a 228.27 5.62771 YES YES 17 a 262.06 1.67508 YES YES 18 a 311.25 0.47589 YES YES 19 a 327.61 1.30239 YES YES 20 a 336.97 1.44098 YES YES 21 a 348.21 13.80850 YES YES 22 a 354.51 9.32063 YES YES 23 a 356.18 8.26212 YES YES 24 a 389.37 6.97586 YES YES 25 a 393.01 39.11064 YES YES 26 a 432.81 1.93965 YES YES 27 a 442.30 48.75422 YES YES 28 a 470.32 60.51817 YES YES 29 a 481.58 19.04053 YES YES 30 a 485.88 3.48738 YES YES

trans-P5S3Br2+ (C1) (MP2/TZVPP)

cycle = 9 MP2 energy = -8042.6503776134 |dE/dxyz| = 0.000225 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P -0.1796064 -0.9033841 -0.1238134 P -1.7560004 -0.0907345 -1.4721447 P -0.2944192 1.6582629 -1.6046963 S -0.4920535 -0.2328587 1.8004246 S -3.0914148 0.5439747 -0.0126693 P -1.7939390 1.4339818 1.4218211 S -0.6459165 2.7010523 0.1959275 P 1.4097287 0.1216954 -1.2657378

48

Br 2.6307392 0.9756026 0.3318137 Br 0.0796416 -3.0446870 0.0523374 Thermodynamics: BP86/SVP your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 40.13 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.63 15.66 11.17 -75.05 77.52 0.52004 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1927190 0.2010333 HOMO-LUMO Separation HOMO: 96. 96 a -0.27682229 H = -7.53272 eV LUMO: 97. 97 a -0.18338049 H = -4.99004 eV Gap : +0.09344180 H = +2.54268 eV Number of MOs= 208, Electrons= 192.00, Symmetry: c1 $vibrational spectrum # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 44.54 0.29567 YES YES 8 a 55.86 0.13279 YES YES 9 a 76.37 0.08811 YES YES 10 a 92.89 0.95715 YES YES 11 a 133.73 0.70649 YES YES 12 a 147.74 0.35330 YES YES 13 a 179.58 1.11055 YES YES 14 a 186.99 1.24063 YES YES 15 a 218.74 4.67449 YES YES 16 a 230.13 7.20969 YES YES 17 a 259.41 1.46032 YES YES 18 a 302.72 0.49259 YES YES 19 a 318.75 1.04323 YES YES 20 a 337.67 1.57199 YES YES 21 a 347.66 5.11393 YES YES 22 a 355.59 14.63138 YES YES 23 a 359.29 3.51818 YES YES 24 a 383.56 11.04379 YES YES 25 a 393.50 9.59902 YES YES 26 a 422.86 40.55784 YES YES 27 a 440.40 7.58355 YES YES 28 a 450.22 92.45927 YES YES 29 a 474.50 7.70297 YES YES 30 a 496.95 4.93576 YES YES

49

P4S3·PI2+ (C1) (MP2/TZVPP)

cycle = 15 MP2 energy = -2920.1443718001 |dE/dxyz| = 0.000417 HOMO-LUMO Separation HOMO: 68. 68 a -0.49354850 H = -13.43015 eV LUMO: 69. 69 a -0.12665186 H = -3.44637 eV Gap : +0.36689664 H = +9.98377 eV Number of MOs= 352, Electrons= 136.00, Symmetry: c1 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P 2.0012723 1.8538913 0.1852670 P 0.8128527 0.0059623 0.4675384 P 1.4181311 0.4821129 -1.6042083 S 3.8441076 1.0867822 0.7778055 S 3.0222192 -0.8442673 -1.7128746 P 3.7507455 -0.9763798 0.2773311 S 1.9406282 -1.5053208 1.2803612 P -1.2870134 -0.0380458 1.2141145 I -1.8971963 1.9320015 -0.0864990 I -1.9623070 -1.9369530 -0.1325533 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 14.77 0.00201 YES YES 8 a 29.39 0.10125 YES YES 9 a 30.79 0.62622 YES YES 10 a 60.44 0.08818 YES YES 11 a 86.81 0.09335 YES YES 12 a 102.00 0.63120 YES YES 13 a 177.71 1.14300 YES YES 14 a 201.27 7.57693 YES YES 15 a 206.42 6.61020 YES YES 16 a 219.71 8.19529 YES YES 17 a 270.18 0.24293 YES YES 18 a 284.59 2.56370 YES YES 19 a 299.65 19.73988 YES YES 20 a 319.17 57.30153 YES YES 21 a 328.81 16.96507 YES YES 22 a 340.84 1.87424 YES YES 23 a 353.54 5.17134 YES YES 24 a 364.39 1.67014 YES YES 25 a 381.56 16.26025 YES YES 26 a 383.09 2.19948 YES YES 27 a 440.42 10.61429 YES YES

50

28 a 458.21 12.00549 YES YES 29 a 472.04 1.79905 YES YES 30 a 504.89 1.28841 YES YES shes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 34.08 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.94 16.24 16.11 -95.54 75.08 0.58057 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1995199 0.2078342

P4S3·PI2+ (C1) MP2/TZVPP

cycle = 15 MP2 energy = -2920.1357861438 |dE/dxyz| = 0.000182 HOMO-LUMO Separation HOMO: 68. 68 a -0.48563299 H = -13.21475 eV LUMO: 69. 69 a -0.12993272 H = -3.53565 eV Gap : +0.35570027 H = +9.67910 eV Number of MOs= 352, Electrons= 136.00, Symmetry: c1 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P 1.2845837 -3.7137029 0.3604400 P 1.6435484 -1.5565930 -0.2221886 P 0.1820877 -2.8233750 -1.3794420 S -0.1218938 -3.6504732 1.9388944 S -1.6927294 -2.2887730 -0.5856084 P -1.3293995 -2.0310496 1.4509307 S 0.3858865 -0.6442295 1.2308661 P -0.8856220 0.9911386 0.2039487 I -0.0173299 1.0226215 -2.0435821 I 0.1598260 2.8700399 1.2896912 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - -

51

6 0.00 0.00000 - - 7 a 13.83 0.02982 YES YES 8 a 35.61 0.13307 YES YES 9 a 48.12 0.27838 YES YES 10 a 56.82 1.23907 YES YES 11 a 71.69 0.35443 YES YES 12 a 98.39 2.13133 YES YES 13 a 160.32 12.24684 YES YES 14 a 178.60 1.88591 YES YES 15 a 209.28 0.16636 YES YES 16 a 237.23 80.02066 YES YES 17 a 267.84 3.29422 YES YES 18 a 277.28 1.76752 YES YES 19 a 287.36 7.40062 YES YES 20 a 317.83 17.44725 YES YES 21 a 319.57 1.67992 YES YES 22 a 326.97 6.07084 YES YES 23 a 332.29 3.19642 YES YES 24 a 341.42 88.66806 YES YES 25 a 382.34 16.38706 YES YES 26 a 406.51 7.32145 YES YES 27 a 414.42 2.83688 YES YES 28 a 428.46 1.58357 YES YES 29 a 450.39 2.38716 YES YES 30 a 461.72 2.92319 YES YES shes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 32.97 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.94 16.22 16.11 -96.59 74.52 0.58221 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.2010420 0.2093563

P4S3·PI2+ (C1) (MP2/TZVPP)

cycle = 8 MP2 energy = -2920.1447568610 |dE/dxyz| = 0.000159 HOMO-LUMO Separation HOMO: 68. 68 a -0.49003239 H = -13.33447 eV LUMO: 69. 69 a -0.13105630 H = -3.56623 eV Gap : +0.35897609 H = +9.76824 eV

52

Number of MOs= 352, Electrons= 136.00, Symmetry: c1 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P 1.1383796 -3.7864383 -0.3038311 P 0.0073128 -3.2847406 1.6115271 P -1.1442766 -3.7840021 -0.2921601 S 0.0115487 -1.1825313 1.6949897 P -0.0003654 -0.8972855 -0.3535884 S -1.6560037 -1.8968040 -1.0785787 S 1.6437193 -1.9010402 -1.0986330 P 0.0001195 1.1938138 -1.1428698 I -1.9396686 1.9175919 0.1196113 I 1.9395690 1.9178456 0.1196086 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 12.10 0.00113 YES YES 8 a 33.09 0.02247 YES YES 9 a 38.46 0.10667 YES YES 10 a 61.42 0.10676 YES YES 11 a 88.61 0.01098 YES YES 12 a 99.13 0.51309 YES YES 13 a 172.81 0.00122 YES YES 14 a 202.60 8.69478 YES YES 15 a 207.80 2.71822 YES YES 16 a 222.98 27.09842 YES YES 17 a 263.73 1.36911 YES YES 18 a 264.03 0.46053 YES YES 19 a 301.27 11.52831 YES YES 20 a 310.41 4.11628 YES YES 21 a 312.65 8.75141 YES YES 22 a 329.37 73.80101 YES YES 23 a 361.72 0.59780 YES YES 24 a 388.94 18.65811 YES YES 25 a 418.53 3.13456 YES YES 26 a 426.01 5.48840 YES YES 27 a 428.22 6.42902 YES YES 28 a 452.22 0.79663 YES YES 29 a 487.08 3.36004 YES YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 34.32 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.94 16.22 15.98 -94.93 75.21 0.57898 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1991776 0.2074919

53

P4S3·PBr2+ (C1) (MP2/TZVPP)

cycle = 11 MP2 energy = -8042.6511521119 |dE/dxyz| = 0.000422 HOMO-LUMO Separation HOMO: 96. 96 a -0.51010640 H = -13.88071 eV LUMO: 97. 97 a -0.12028346 H = -3.27308 eV Gap : +0.38982294 H = +10.60763 eV Number of MOs= 392, Electrons= 192.00, Symmetry: c1 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P 1.5257960 1.8562537 0.1995445 P 0.3525606 -0.0062074 0.4327498 P 1.0038423 0.5063105 -1.6174632 S 3.3558841 1.0938930 0.8404145 S 2.6201182 -0.8086456 -1.7009281 P 3.2954708 -0.9594117 0.3045551 S 1.4633396 -1.5210150 1.2552198 P -1.8028242 -0.0616472 1.0879214 Br -2.3093755 1.7269552 -0.1132416 Br -2.3714571 -1.7486749 -0.2030147 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 11.98 0.00780 YES YES 8 a 26.93 0.51836 YES YES 9 a 29.11 0.26602 YES YES 10 a 71.10 0.58978 YES YES 11 a 101.61 0.40280 YES YES 12 a 129.74 1.52558 YES YES 13 a 178.16 1.31747 YES YES 14 a 202.79 5.50604 YES YES 15 a 207.87 5.79193 YES YES 16 a 223.83 12.88153 YES YES 17 a 271.85 0.07980 YES YES 18 a 287.10 1.27747 YES YES 19 a 326.48 3.55172 YES YES 20 a 339.91 0.43856 YES YES 21 a 352.60 4.86419 YES YES 22 a 361.26 17.62778 YES YES 23 a 371.80 33.14079 YES YES 24 a 378.32 15.10639 YES YES 25 a 384.07 9.55946 YES YES 26 a 399.79 61.36148 YES YES 27 a 438.85 13.39721 YES YES 28 a 457.47 7.98803 YES YES 29 a 472.06 1.68183 YES YES

54

30 a 508.02 0.88303 YES YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 35.17 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.63 15.81 15.79 -91.82 75.50 0.56953 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1982776 0.2065919

P4S3·PBr2+ (C1) (MP2/TZVPP)

cycle = 11 MP2 energy = -8042.6459259522 |dE/dxyz| = 0.000376 HOMO-LUMO Separation HOMO: 96. 96 a -0.49906579 H = -13.58028 eV LUMO: 97. 97 a -0.13109597 H = -3.56730 eV Gap : +0.36796982 H = +10.01297 eV Number of MOs= 392, Electrons= 192.00, Symmetry: c1 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P 1.2663071 -3.2355681 0.0474363 P 1.6509754 -1.0473157 -0.3732946 P 0.1664320 -2.2096840 -1.6163480 S -0.1294664 -3.2720502 1.6348514 S -1.7004274 -1.7188788 -0.7744002 P -1.3269993 -1.6130429 1.2733042 S 0.4027923 -0.2288796 1.1447697 P -0.8290343 1.4965176 0.2170833 Br -0.0529820 1.5434903 -1.8292665 Br 0.2660342 3.1127646 1.1997897 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 17.37 0.04501 YES YES

55

8 a 39.24 0.14820 YES YES 9 a 56.03 0.43173 YES YES 10 a 72.92 1.26957 YES YES 11 a 85.27 0.46497 YES YES 12 a 132.94 2.59998 YES YES 13 a 174.16 5.94065 YES YES 14 a 181.89 4.21447 YES YES 15 a 211.54 0.25482 YES YES 16 a 243.46 60.48022 YES YES 17 a 269.88 4.43999 YES YES 18 a 278.09 1.85231 YES YES 19 a 296.23 9.70235 YES YES 20 a 318.11 4.57113 YES YES 21 a 322.88 4.98054 YES YES 22 a 331.78 0.35158 YES YES 23 a 380.04 12.00009 YES YES 24 a 394.94 29.32512 YES YES 25 a 404.46 44.66319 YES YES 26 a 410.62 61.53745 YES YES 27 a 417.69 10.97918 YES YES 28 a 428.59 1.19280 YES YES 29 a 450.37 3.55151 YES YES 30 a 462.96 2.52442 YES YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 34.35 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.63 15.75 14.80 -90.04 75.01 0.56188 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1996245 0.2079388

P4S3·PBr2+ (C1) (MP2/TZVPP)

cycle = 9 MP2 energy = -8042.6516523313 |dE/dxyz| = 0.000082 HOMO-LUMO Separation HOMO: 96. 96 a -0.49873015 H = -13.57115 eV LUMO: 97. 97 a -0.12508530 H = -3.40375 eV Gap : +0.37364485 H = +10.16740 eV Number of MOs= 392, Electrons= 192.00, Symmetry: c1

56

xyz-coordinates of the MP2/TZVPP structure in Angstrom units P 1.1399524 -3.3138113 -0.3344557 P 0.0030053 -2.8512868 1.5869316 P -1.1427435 -3.3126373 -0.3295168 S 0.0052458 -0.7486024 1.7127887 P -0.0000297 -0.4366831 -0.3283902 S -1.6551296 -1.4086021 -1.0817417 S 1.6499882 -1.4105729 -1.0904219 P 0.0000064 1.7108456 -1.0315621 Br -1.7420629 2.3055639 0.1768826 Br 1.7419469 2.3058446 0.1768289 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 a -6.22 0.00000 YES YES 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 0.00 0.20947 - - 8 a 34.77 0.13482 YES YES 9 a 38.79 0.19997 YES YES 10 a 71.83 0.90919 YES YES 11 a 100.01 0.18069 YES YES 12 a 129.48 1.87529 YES YES 13 a 173.16 0.00032 YES YES 14 a 204.17 7.78058 YES YES 15 a 209.01 2.67909 YES YES 16 a 232.78 30.89664 YES YES 17 a 263.80 0.68715 YES YES 18 a 264.00 0.58946 YES YES 19 a 306.82 1.00669 YES YES 20 a 311.55 0.11475 YES YES 21 a 364.02 2.49003 YES YES 22 a 378.70 24.15643 YES YES 23 a 389.58 26.15927 YES YES 24 a 398.37 79.45609 YES YES 25 a 419.48 4.31391 YES YES 26 a 425.62 4.07786 YES YES 27 a 428.93 4.51264 YES YES 28 a 453.17 1.98968 YES YES 29 a 489.66 5.07833 YES YES 30 a 493.60 6.22600 YES YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 imaginary frequency not included in vib. partition sum zero point vibrational energy ----------------------------- zpe= 35.43 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.63 15.77 12.30 -82.82 73.18 0.53157 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1895456 0.1978599

57

P5S3I2+ (Cs) (MP2/TZVPP)

2.219

2.363

2.377

2.326

2.106

2.1272.124

2.067

2.219

2.363

2.377

2.326

2.106

2.1272.124

2.067

cycle = 31 SCF+MP2 energy = -2920.1467801637 |dE/dxyz| = 0.000337 HOMO-LUMO Separation HOMO: 68. 24 a" -0.48704621 H = -13.25321 eV LUMO: 69. 45 a' -0.14662288 H = -3.98981 eV Gap : +0.34042333 H = +9.26340 eV Number of MOs= 352, Electrons= 136.00, Symmetry: cs xyz-coordinates of the MP2/TZVPP structure in Angstrom units P 2.1169317 1.5316230 0.0000000 P 0.7345335 0.7508244 -1.6998567 P 0.7345335 0.7508244 1.6998567 S 1.5999314 3.5333161 0.0000000 S -0.7962877 2.1973908 -1.7097462 S -0.7962877 2.1973908 1.7097462 P -0.5221005 3.4323986 0.0000000 P 0.0487967 -0.4996868 0.0000000 I -2.2456610 -1.0650802 0.0000000 I 1.4840786 -2.3941937 0.0000000 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a' 30.80 0.09348 YES YES 8 a" 44.09 0.01120 YES YES 9 a' 62.02 0.38261 YES YES 10 a" 83.27 0.73581 YES YES 11 a' 111.31 0.31705 YES YES 12 a' 129.06 0.41169 YES YES 13 a" 138.37 0.15937 YES YES 14 a' 191.72 3.58130 YES YES 15 a" 213.45 1.39657 YES YES 16 a" 228.52 1.67204 YES YES 17 a' 254.28 9.26765 YES YES 18 a" 291.76 0.99377 YES YES 19 a' 293.79 18.09266 YES YES 20 a' 312.85 2.91312 YES YES 21 a" 339.44 3.99095 YES YES 22 a' 345.39 8.40480 YES YES 23 a' 353.38 11.51568 YES YES 24 a' 378.70 55.17454 YES YES

58

25 a' 384.55 3.46270 YES YES 26 a' 424.36 44.72325 YES YES 27 a" 431.48 3.37366 YES YES 28 a" 436.47 8.40863 YES YES 29 a' 437.71 20.57011 YES YES 30 a' 478.53 1.49540 YES YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 34.43 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.94 16.08 13.93 -89.38 74.98 0.55961 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1997104 0.2080247

59

P5S3I2+ (C1) (MP2/TZVPP)

2.257

2.277

2.219

2.102

2.0902.087

2.133

2.2092.040

2.188

2.381

2.389

2.257

2.277

2.219

2.102

2.0902.087

2.133

2.2092.040

2.188

2.381

2.389

cycle = 13 SCF+MP2 energy = -2920.1269398920 |dE/dxyz| = 0.000258 HOMO-LUMO Separation HOMO: 68. 68 a -0.48344876 H = -13.15532 eV LUMO: 69. 69 a -0.14666105 H = -3.99085 eV Gap : +0.33678771 H = +9.16447 eV Number of MOs= 352, Electrons= 136.00, Symmetry: c1 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P -0.1270529 -0.4295348 -0.1413546 P -1.7468660 2.5155880 -0.1475072 S -1.9616237 0.3566532 -0.5628471 P 1.5898520 2.4659743 0.7453958 P 1.3937326 2.6845815 -1.4544599 P 1.7355713 0.6277539 -0.5902872 S -0.4123569 2.6786915 1.4483585 S -0.6188215 3.2070613 -1.7658839 I 0.0403419 -2.3598753 -1.5252777 I 0.0213851 -1.1368286 2.1353551 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 a -5.44 0.00000 YES YES 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 0.00 0.34581 - - 8 a 46.26 0.00881 YES YES 9 a 56.80 0.82993 YES YES 10 a 94.42 0.42931 YES YES 11 a 102.80 0.56920 YES YES 12 a 109.45 0.33693 YES YES 13 a 129.86 0.51238 YES YES 14 a 160.95 2.30903 YES YES 15 a 174.22 0.52787 YES YES 16 a 200.41 9.10180 YES YES 17 a 263.79 10.19724 YES YES 18 a 270.48 1.18764 YES YES 19 a 281.32 27.11305 YES YES 20 a 302.46 3.36593 YES YES 21 a 317.15 3.04727 YES YES 22 a 339.49 15.98889 YES YES 23 a 358.58 60.77280 YES YES 24 a 368.12 38.23036 YES YES 25 a 399.85 29.60491 YES YES 26 a 402.92 9.28486 YES YES 27 a 418.69 7.75154 YES YES 28 a 450.71 5.71721 YES YES 29 a 457.55 16.52451 YES YES 30 a 530.03 35.49605 YES YES

60

your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 imaginary frequency not included in vib. partition sum zero point vibrational energy ----------------------------- zpe= 33.57 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.94 16.10 12.41 -86.52 72.39 0.54130 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1918813 0.2001956

P5S3I2+ (C1) (MP2/TZVPP)

2.305

2.2112.234 2.183

2.109

2.036

2.267

2.080

2.148

2.088

2.382

2.374

2.305

2.2112.234 2.183

2.109

2.036

2.267

2.080

2.148

2.088

2.382

2.374

cycle = 17 SCF+MP2 energy = -2920.1242891301 |dE/dxyz| = 0.000309 HOMO-LUMO Separation HOMO: 68. 68 a -0.47414847 H = -12.90224 eV LUMO: 69. 69 a -0.14231726 H = -3.87265 eV Gap : +0.33183121 H = +9.02959 eV Number of MOs= 352, Electrons= 136.00, Symmetry: c1 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P -0.8354175 -0.7410197 -1.6532007 S -2.3119969 -1.8222453 -0.6653068 P -1.4019036 -3.4011231 0.4722630 P 0.7276550 -3.2445520 -0.1006265 P 0.1117002 -2.3330690 1.8440766 S 0.7539783 -2.0793371 -1.8586448 P -0.1078312 0.4526266 0.1319454 I -1.2987616 2.4990901 -0.0407969 I 2.2417544 0.8283139 0.0250886 S -0.7195917 -0.3156837 1.9152769 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - -

61

3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 26.21 0.04708 YES YES 8 a 47.54 0.09960 YES YES 9 a 64.90 0.75517 YES YES 10 a 84.78 0.76110 YES YES 11 a 108.50 0.27997 YES YES 12 a 113.78 1.30620 YES YES 13 a 127.34 0.50459 YES YES 14 a 153.68 0.95612 YES YES 15 a 162.05 0.72562 YES YES 16 a 224.64 0.56671 YES YES 17 a 249.44 30.36144 YES YES 18 a 269.64 0.04842 YES YES 19 a 283.69 0.81817 YES YES 20 a 302.39 8.77454 YES YES 21 a 324.06 8.05847 YES YES 22 a 347.12 9.97017 YES YES 23 a 365.85 30.05383 YES YES 24 a 381.00 37.90681 YES YES 25 a 385.81 9.55310 YES YES 26 a 397.21 26.62203 YES YES 27 a 418.55 5.05858 YES YES 28 a 455.38 3.12284 YES YES 29 a 463.30 1.55012 YES YES 30 a 509.70 56.57237 YES YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 33.73 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.94 16.09 14.54 -91.63 74.86 0.56672 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.2001907 0.2085050

62

P5S3Br2+ (Cs) (MP2/TZVPP)

2.2072.136

2.157

2.327

2.111

2.1242.117

2.068

2.2072.136

2.157

2.327

2.111

2.1242.117

2.068

cycle = 3 MP2 energy = -8042.6505772060 |dE/dxyz| = 0.000147 HOMO-LUMO Separation HOMO: 96. 32 a" -0.49587923 H = -13.49357 eV LUMO: 97. 65 a' -0.13997552 H = -3.80893 eV Gap : +0.35590371 H = +9.68464 eV Number of MOs= 392, Electrons= 192.00, Symmetry: cs xyz-coordinates of the MP2/TZVPP structure in Angstrom units P 1.9463878 1.2413413 0.0000000 P 0.6286197 0.3576791 -1.7055518 P 0.6286197 0.3576791 1.7055518 S 1.2750016 3.1967734 0.0000000 S -1.0156754 1.6806246 -1.7077276 S -1.0156754 1.6806246 1.7077276 P -0.8314666 2.9309780 0.0000000 P 0.0311158 -0.9118060 0.0000000 Br -2.0071754 -1.5750626 0.0000000 Br 1.3791232 -2.5974873 0.0000000 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a' 33.89 0.20488 YES YES 8 a" 49.82 0.00581 YES YES 9 a' 82.25 0.44939 YES YES 10 a" 94.72 1.02685 YES YES 11 a' 127.94 0.04902 YES YES 12 a" 142.91 0.70466 YES YES 13 a' 158.40 0.20074 YES YES 14 a' 199.36 3.18089 YES YES 15 a" 213.24 1.36385 YES YES 16 a" 227.97 1.60732 YES YES 17 a' 270.35 1.33869 YES YES 18 a" 289.14 0.68994 YES YES 19 a' 300.12 19.74905 YES YES 20 a' 314.81 1.42833 YES YES 21 a" 343.95 6.88383 YES YES 22 a' 351.87 16.60069 YES YES 23 a' 358.86 5.00765 YES YES 24 a' 382.10 4.32172 YES YES 25 a' 428.35 9.81588 YES YES 26 a" 435.76 4.06416 YES YES 27 a' 440.95 73.46624 YES YES

63

28 a" 454.73 3.72248 YES YES 29 a' 475.52 18.34340 YES YES 30 a' 487.70 42.29976 YES YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 35.88 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.63 15.61 12.92 -83.51 75.56 0.54183 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1981071 0.2064214

P5S3Br2+ (C1) (MP2/TZVPP)

2.259

2.280

2.214

2.100

2.0862.088

2.129

2.2142.025

2.177

2.160

2.259

2.280

2.214

2.100

2.0862.088

2.129

2.2142.025

2.177

2.160

cycle = 15 MP2 energy = -8042.6351635355 |dE/dxyz| = 0.000125 HOMO-LUMO Separation HOMO: 96. 96 a -0.49281937 H = -13.41030 eV LUMO: 97. 97 a -0.13322152 H = -3.62514 eV Gap : +0.35959785 H = +9.78516 eV Number of MOs= 392, Electrons= 192.00, Symmetry: c1 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P -0.1037664 -0.8491081 -0.1293383 P -1.7558527 2.0434036 0.0781062 S -1.9488986 -0.0943320 -0.4897715 P 1.5839400 1.9682393 0.9458554 P 1.3718207 2.3420818 -1.2297068 P 1.7485463 0.2298603 -0.5203052 S -0.4146467 2.1081366 1.6734444 S -0.6485606 2.8509489 -1.4988134 Br 0.0665721 -2.5606508 -1.4330635 Br 0.0394156 -1.6141230 1.8910758 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - -

64

5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 14.65 0.12407 YES YES 8 a 57.42 0.07702 YES YES 9 a 81.30 0.63546 YES YES 10 a 109.57 1.25384 YES YES 11 a 122.42 0.37826 YES YES 12 a 134.09 0.81643 YES YES 13 a 140.48 0.57078 YES YES 14 a 165.58 0.78062 YES YES 15 a 178.95 0.89929 YES YES 16 a 216.43 7.44671 YES YES 17 a 271.81 6.23277 YES YES 18 a 274.04 18.18145 YES YES 19 a 289.64 10.45297 YES YES 20 a 306.19 1.56896 YES YES 21 a 328.40 0.73266 YES YES 22 a 350.65 3.89649 YES YES 23 a 380.77 16.71528 YES YES 24 a 400.96 7.44400 YES YES 25 a 414.32 12.01172 YES YES 26 a 432.10 69.26814 YES YES 27 a 437.94 53.13141 YES YES 28 a 452.50 17.93671 YES YES 29 a 459.20 24.68602 YES YES 30 a 550.55 42.91133 YES YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 35.37 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.63 15.65 13.95 -86.65 75.51 0.55221 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1983802 0.2066945

65

P5S3Br2+ (C1) (MP2/TZVPP)

2.296

2.2142.231 2.189

2.111

2.026

2.248

2.081

2.146

2.087

2.157

2.151

2.296

2.2142.231 2.189

2.111

2.026

2.248

2.081

2.146

2.087

2.157

2.151

cycle = 16 MP2 energy = -8042.6303534345 |dE/dxyz| = 0.000439 HOMO-LUMO Separation HOMO: 96. 96 a -0.48230188 H = -13.12411 eV LUMO: 97. 97 a -0.12611029 H = -3.43164 eV Gap : +0.35619159 H = +9.69247 eV Number of MOs= 392, Electrons= 192.00, Symmetry: c1 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P -0.5935026 -0.3853622 -1.6809731 S -2.0248601 -1.5876065 -0.7713444 P -1.0450886 -3.0761424 0.4284808 P 1.0959475 -2.7527225 -0.0384466 P 0.3036407 -1.9010506 1.8682422 S 1.1238964 -1.5695544 -1.7850675 P -0.0727834 0.8515221 0.1254591 Br -1.2693606 2.6290536 -0.0849552 Br 2.0079868 1.4228055 0.0728130 S -0.6386344 0.0760140 1.9078045 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 25.89 0.08174 YES YES 8 a 56.48 0.26003 YES YES 9 a 85.02 1.30137 YES YES 10 a 99.44 0.86545 YES YES 11 a 123.79 0.53841 YES YES 12 a 126.02 0.08887 YES YES 13 a 140.48 0.85029 YES YES 14 a 164.03 1.19008 YES YES 15 a 167.73 0.74868 YES YES 16 a 232.86 3.83165 YES YES 17 a 269.34 12.40053 YES YES 18 a 271.42 4.21194 YES YES 19 a 287.04 1.40496 YES YES 20 a 301.05 7.96841 YES YES 21 a 329.56 5.06579 YES YES 22 a 349.67 11.35241 YES YES 23 a 385.84 0.11495 YES YES 24 a 395.79 2.96310 YES YES 25 a 416.13 2.17330 YES YES 26 a 420.86 51.30732 YES YES 27 a 450.57 32.29699 YES YES

66

28 a 459.24 44.11148 YES YES 29 a 465.08 2.12437 YES YES 30 a 531.22 69.54605 YES YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 35.28 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.63 15.64 13.52 -85.65 75.46 0.54870 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1984984 0.2068127

67

P5S2X2+ at the MP2/TZVPP level

P5S2Br2+ (Cs)

P1

P2

P3

P4P5

S1

S2

Br1

Br2

2.2532.226

2.1782.136

2.085

2.227 2.155

P1

P2

P3

P4P5

S1

S2

Br1

Br2

2.2532.226

2.1782.136

2.085

2.227 2.155

cycle = 8 MP2 energy = -7644.9278303154 |dE/dxyz| = 0.000186 HOMO-LUMO Separation HOMO: 88. 37 a" -0.51013917 H = -13.88160 eV LUMO: 89. 52 a' -0.12176785 H = -3.31347 eV Gap : +0.38837131 H = +10.56813 eV Number of MOs= 355, Electrons= 176.00, Symmetry: cs xyz-coordinates of the MP2/TZVPP structure in Angstrom units P 0.0489992 -0.5601779 0.0000000 P -1.7598323 0.7383868 0.0000000 P 0.9308791 2.3842552 1.1130049 P 0.9308791 2.3842552 -1.1130049 P 1.8555497 0.6568997 0.0000000 S -1.0599257 1.8180431 1.6405173 S -1.0599257 1.8180431 -1.6405173 Br 0.0364337 -1.8155204 -1.7510017 Br 0.0364337 -1.8155204 1.7510017 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a" 53.22 0.27172 YES YES 8 a" 57.27 0.14748 YES YES 9 a' 93.67 0.61464 YES YES 10 a' 110.14 0.97224 YES YES 11 a" 150.70 0.16825 YES YES 12 a' 169.06 0.22081 YES YES 13 a" 175.70 1.01121 YES YES 14 a' 203.41 5.21209 YES YES 15 a" 273.36 0.05918 YES YES 16 a' 277.84 7.04608 YES YES 17 a' 323.41 11.28616 YES YES 18 a" 326.80 1.79249 YES YES 19 a' 333.13 3.92478 YES YES 20 a' 367.10 3.52283 YES YES 21 a" 385.50 3.90541 YES YES 22 a' 418.66 16.57812 YES YES 23 a' 432.11 1.65910 YES YES 24 a" 447.86 18.82500 YES YES 25 a' 449.72 73.36199 YES YES 26 a" 466.90 53.07773 YES YES 27 a' 468.08 0.54455 YES YES your wishes are: panf= 0.1000 pend= 0.1000 nump= 1

68

tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 32.21 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.51 15.32 10.62 -80.45 67.34 0.50399 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1755809 0.1838952 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 243.2 tend= 243.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 32.21 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 243.15 0.1000000 19.00 15.02 8.48 -53.71 57.93 0.46744 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 243.15 0.1000000 0.1657849 0.1740992 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 193.2 tend= 193.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 32.21 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 193.15 0.1000000 18.42 14.67 6.44 -31.27 49.97 0.42895 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 193.15 0.1000000 0.1514171 0.1597314 shes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 32.21 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.51 15.32 10.62 -80.45 67.34 0.50399

69

P1

P2

P3

P4P5

S1

S2 I1

I2

2.084

2.233

2.2292.251

2.133

2.182

2.376

P1

P2

P3

P4P5

S1

S2 I1

I2

2.084

2.233

2.2292.251

2.133

2.182

2.376

T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1755809 0.1838952

P5S2I2

+ (Cs) (MP2/TZVPP) cycle = 8 SCF+MP2 energy = -2522.4242580799 |dE/dxyz| = 0.000131 HOMO-LUMO Separation HOMO: 60. 23 a" -0.49943438 H = -13.59031 eV LUMO: 61. 38 a' -0.13930244 H = -3.79061 eV Gap : +0.36013194 H = +9.79969 eV Number of MOs= 315, Electrons= 120.00, Symmetry: cs xyz-coordinates of the MP2/TZVPP structure in Angstrom units P 0.0358736 -0.1637577 0.0000000 P -1.7537231 1.1710356 0.0000000 P 0.9413698 2.8032585 1.1144713 P 0.9413698 2.8032585 -1.1144713 P 1.8387809 1.0651716 0.0000000 S -1.0523784 2.2548375 1.6365526 S -1.0523784 2.2548375 -1.6365526 I 0.0213769 -1.5068280 -1.9594922 I 0.0213769 -1.5068280 1.9594922 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a" 42.26 0.09001 YES YES 8 a" 48.61 0.12908 YES YES 9 a' 62.77 0.59709 YES YES 10 a' 92.44 0.66669 YES YES 11 a" 130.31 0.64138 YES YES 12 a' 135.08 0.20793 YES YES 13 a" 173.75 1.02952 YES YES 14 a' 201.81 6.67163 YES YES 15 a' 268.65 15.05757 YES YES 16 a" 273.10 0.08986 YES YES 17 a' 317.35 19.14607 YES YES 18 a" 324.35 3.59848 YES YES 19 a' 333.32 3.29990 YES YES 20 a' 365.22 10.16617 YES YES 21 a' 365.85 6.53089 YES YES 22 a" 383.59 57.97213 YES YES 23 a" 390.63 9.90366 YES YES

70

24 a' 422.85 11.71902 YES YES 25 a' 432.54 17.92578 YES YES 26 a" 457.69 8.09566 YES YES 27 a' 464.54 4.24436 YES YES ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 243.2 tend= 243.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 30.61 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 243.15 0.1000000 19.33 15.50 9.67 -59.35 57.23 0.48779 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 243.15 0.1000000 0.1680252 0.1763395 ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 193.2 tend= 193.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 30.61 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 193.15 0.1000000 18.76 15.16 7.51 -35.92 49.14 0.44870 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 193.15 0.1000000 0.1543525 0.1626668 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 30.61 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.84 15.81 11.88 -87.23 66.75 0.52473 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1772571 0.1855714

71

2.049

2.150

2.0582.110 2.139

2.106

2.0602.113

2.193

2.159

2.304

S

Br

S

P

SS

P

P

P 2.049

2.150

2.0582.110 2.139

2.106

2.0602.113

2.193

2.159

2.304

S

Br

S

P

SS

P

P

P

P4S4X+ at the MP2/TZVPP level

P4S4Br+ (C1) (MP2/TZVPP) cycle = 8 MP2 energy = -5526.8839018467 |dE/dxyz| = 0.000293 HOMO-LUMO Separation HOMO: 79. 79 a -0.51363271 H = -13.97667 eV LUMO: 80. 80 a -0.12447346 H = -3.38710 eV Gap : +0.38915925 H = +10.58957 eV Number of MOs= 344, Electrons= 158.00, Symmetry: c1 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P -1.5505975 -1.7738150 -0.4439705 S 0.3841969 -2.1062231 0.5403156 P 0.7508752 -0.1397470 0.0872873 Br 2.8634110 0.2358315 -0.0528049 P -0.5171960 -0.1635541 -1.7331681 S -2.7197238 -0.5965032 0.8548568 P -2.0003106 1.3863941 0.7295847 S -1.6365489 1.5306508 -1.3761327 S 0.0404041 1.2515796 1.4265756 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 67.50 0.16638 YES YES 8 a 94.20 0.23528 YES YES 9 a 141.94 0.39152 YES YES 10 a 150.49 0.50785 YES YES 11 a 173.35 0.12875 YES YES 12 a 206.78 2.13196 YES YES 13 a 214.38 3.20987 YES YES 14 a 220.69 2.14340 YES YES 15 a 264.31 1.78186 YES YES 16 a 300.73 1.52062 YES YES 17 a 310.37 1.08416 YES YES 18 a 328.74 1.32926 YES YES 19 a 347.36 5.19744 YES YES 20 a 358.48 16.95632 YES YES 21 a 369.85 21.29210 YES YES 22 a 390.00 17.48032 YES YES 23 a 427.32 9.74452 YES YES 24 a 463.96 36.55271 YES YES 25 a 483.85 50.92800 YES YES 26 a 494.06 25.94928 YES YES 27 a 542.29 39.62078 YES YES

72

------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 34.19 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.31 15.06 8.97 -73.26 68.00 0.48210 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1737465 0.1820608 ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 243.2 tend= 243.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 34.19 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 243.15 0.1000000 18.80 14.76 6.95 -47.71 58.71 0.44599 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 243.15 0.1000000 0.1633392 0.1716535 ------------------ your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 193.2 tend= 193.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 34.19 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 193.15 0.1000000 18.23 14.41 5.05 -26.34 50.89 0.40815 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 193.15 0.1000000 0.1481781 0.1564924

73

P4S4I+ (C1)

2.305

2.190

2.058

2.062

2.3652.224

2.154

2.059

2.1392.109

I

S

S

S

PP

P

P

P4S4I+ (C1)

2.305

2.190

2.058

2.062

2.3652.224

2.154

2.059

2.1392.109

I

S

S

S

PP

P

P

P4S4I+ (C1) (MP2/TZVPP)

cycle = 5 MP2 energy = -2965.6310299414 |dE/dxyz| = 0.000310 HOMO-LUMO Separation HOMO: 65. 65 a -0.50720947 H = -13.80188 eV LUMO: 66. 66 a -0.13501961 H = -3.67407 eV Gap : +0.37218986 H = +10.12781 eV Number of MOs= 324, Electrons= 130.00, Symmetry: c1 xyz-coordinates of the MP2/TZVPP structure in Angstrom units P -1.1567332 -1.6951666 -0.4551422 S 0.7515518 -2.0964254 0.5437604 P 1.2271722 -0.1440557 0.0933343 I 3.5667324 0.1745827 -0.0369250 P -0.0479004 -0.1288219 -1.7318952 S -2.2907973 -0.4706644 0.8320272 P -1.4894617 1.4803695 0.7165805 S -1.0999681 1.6080986 -1.3872639 S 0.5379723 1.2719325 1.4253205 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 52.14 0.71941 YES YES 8 a 76.80 0.32889 YES YES 9 a 103.96 5.11252 YES YES 10 a 137.41 0.63939 YES YES 11 a 161.77 0.09949 YES YES 12 a 205.95 1.90393 YES YES 13 a 212.73 2.26588 YES YES 14 a 214.75 5.29836 YES YES 15 a 251.65 3.78435 YES YES 16 a 297.54 1.24159 YES YES 17 a 308.23 0.68257 YES YES 18 a 327.15 0.52929 YES YES 19 a 345.22 7.12255 YES YES 20 a 355.22 22.94367 YES YES 21 a 368.10 27.99774 YES YES 22 a 388.89 16.72517 YES YES 23 a 417.29 39.89655 YES YES 24 a 427.18 39.68523 YES YES 25 a 461.64 8.30624 YES YES 26 a 494.20 9.04731 YES YES 27 a 527.41 33.54811 YES YES your wishes are :

74

------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 33.03 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.51 15.35 9.84 -77.78 67.57 0.49581 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.1749338 0.1832481 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 243.2 tend= 243.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 33.03 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 243.15 0.1000000 19.00 15.04 7.76 -51.48 58.20 0.45942 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 243.15 0.1000000 0.1649153 0.1732296 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 193.2 tend= 193.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 33.03 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 193.15 0.1000000 18.42 14.70 5.78 -29.45 50.30 0.42116 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 193.15 0.1000000 0.1502337 0.1585480

75

P

P

BrBr

2.050

2.233

96.6°

Small particles P2Br2 (C2h) (MP2/TZVPP) cycle = 6 MP2 energy = -5826.9611166344 |dE/dxyz| = 0.000014 HOMO-LUMO Separation HOMO: 50. 7 au -0.34384154 H = -9.35641 eV LUMO: 51. 7 bg -0.01592304 H = -0.43329 eV Gap : +0.32791850 H = +8.92312 eV Number of MOs= 170, Electrons= 100.00, Symmetry: c2h xyz-coordinates of the MP2/TZVPP structure in Angstrom units Br 2.5594949 0.0709159 0.0000000 P 0.5361295 -0.8734323 0.0000000 P -0.5361295 0.8734323 0.0000000 Br -2.5594949 -0.0709159 0.0000000 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 a 87.44 0.87034 YES YES 8 a 92.13 0.26105 YES YES 9 a 138.43 0.00000 YES YES 10 a 375.35 0.00021 YES YES 11 a 379.96 96.52975 YES YES 12 a 590.11 0.00006 YES YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 8.954 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 18.71 13.32 3.57 -79.28 24.74 0.35718 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.0677257 0.0760400 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1

76

P

P I

I

2.050

2.445

96.5°

tanf= 243.2 tend= 243.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 8.954 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 243.15 0.1000000 18.20 13.01 2.92 -60.04 21.08 0.34194 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 243.15 0.1000000 0.0650754 0.0733897 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 193.2 tend= 193.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 8.954 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 193.15 0.1000000 17.62 12.67 2.28 -43.34 17.91 0.32545 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 193.15 0.1000000 0.0614117 0.0697260

P2I2 (C2h) (MP2/TZVPP) cycle = 3 MP2 energy = -704.4507534443 |dE/dxyz| = 0.000152 HOMO-LUMO Separation HOMO: 22. 3 au -0.32884220 H = -8.94826 eV LUMO: 23. 3 bg -0.01866192 H = -0.50782 eV Gap : +0.31018028 H = +8.44044 eV Number of MOs= 130, Electrons= 44.00, Symmetry: c2h xyz-coordinates of the MP2/TZVPP structure in Angstrom units I 2.7572420 0.0395283 0.0000000 P 0.4985637 -0.8956608 0.0000000 P -0.4985637 0.8956608 0.0000000 I -2.7572420 -0.0395283 0.0000000 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - -

77

5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 au 73.13 0.06388 YES NO 8 bu 74.97 0.87003 YES NO 9 ag 101.17 0.00000 NO YES 10 bu 307.68 91.22265 YES NO 11 ag 313.20 0.00000 NO YES 12 ag 588.03 0.00000 NO YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 7.850 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 19.24 13.26 4.30 -83.35 24.34 0.36953 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.0688929 0.0772072 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 243.2 tend= 243.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 7.850 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 243.15 0.1000000 18.73 12.95 3.59 -63.44 20.61 0.35400 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 243.15 0.1000000 0.0666723 0.0749866 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 193.2 tend= 193.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 7.850 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 193.15 0.1000000 18.15 12.61 2.87 -46.15 17.35 0.33708 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 193.15 0.1000000 0.0635769 0.0718912

78

2.238 2.246

PBr

Br

Br

Br

Br

Br P

PP P

P

91.3°96.0°

P6Br6 (D3d) (MP2/TZVPP) cycle = 6 MP2 energy = -17481.0027785871 |dE/dxyz| = 0.000449 HOMO-LUMO Separation HOMO: 100. 19 a1g -0.36590099 H = -9.95668 eV LUMO: 101. 20 a1g -0.01941995 H = -0.52844 eV Gap : +0.34648104 H = +9.42823 eV Number of MOs= 340, Electrons= 300.00, Symmetry: d3d xyz-coordinates of the MP2/TZVPP structure in Angstrom units P -1.6053496 0.9268490 -0.6338580 P -1.6053496 -0.9268490 0.6338580 P 0.0000000 -1.8536980 -0.6338580 P 1.6053496 -0.9268490 0.6338580 P 1.6053496 0.9268490 -0.6338580 P 0.0000000 1.8536980 0.6338580 Br -3.3219133 1.9179076 0.4046670 Br -3.3219133 -1.9179076 -0.4046670 Br 0.0000000 3.8358151 -0.4046670 Br 0.0000000 -3.8358151 0.4046670 Br 3.3219133 1.9179076 0.4046670 Br 3.3219133 -1.9179076 -0.4046670 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 eu 19.87 0.05791 YES NO 8 eu 19.87 0.05791 YES NO 9 a1g 33.65 0.00000 NO YES 10 eg 49.08 0.00000 NO YES 11 eg 49.08 0.00000 NO YES 12 a1u 58.22 0.00000 NO NO 13 a2u 60.25 1.18897 YES NO 14 eu 65.03 0.14571 YES NO 15 eu 65.03 0.14571 YES NO 16 eg 93.16 0.00000 NO YES 17 eg 93.16 0.00000 NO YES 18 a1g 112.38 0.00000 NO YES 19 eg 128.48 0.00000 NO YES 20 eg 128.48 0.00000 NO YES 21 a2u 151.21 1.24953 YES NO 22 a2g 159.28 0.00000 NO NO 23 eu 177.48 10.54527 YES NO 24 eu 177.48 10.54527 YES NO 25 a1u 339.67 0.00000 NO NO 26 eg 366.30 0.00000 NO YES 27 eg 366.30 0.00000 NO YES 28 eu 367.85 80.81887 YES NO 29 eu 367.85 80.81887 YES NO 30 eg 378.35 0.00000 NO YES

79

31 eg 378.35 0.00000 NO YES 32 a2u 386.16 8.26093 YES NO 33 a1g 388.04 0.00000 NO YES 34 eu 424.31 0.07750 YES NO 35 eu 424.31 0.07750 YES NO 36 a1g 447.57 0.00000 NO YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 33.79 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 20.35 15.40 26.08 -119.51 89.26 0.70854 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.2513676 0.2596819 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 243.2 tend= 243.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 33.79 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 243.15 0.1000000 19.84 15.10 22.30 -81.93 75.68 0.65652 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 243.15 0.1000000 0.2417718 0.2500861 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 193.2 tend= 193.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 33.79 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 193.15 0.1000000 19.27 14.75 18.44 -50.46 63.92 0.60052 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 193.15 0.1000000 0.2274894 0.2358037

80

2.244

2.447

P

P

PP

P

P

I

II

I

I

I

92.3° 94.8°

P6I6 (D3d) (MP2/TZVPP) cycle = 6 MP2 energy = -2113.4834399752 |dE/dxyz| = 0.000001 HOMO-LUMO Separation HOMO: 44. 11 eu -0.35102502 H = -9.55188 eV LUMO: 45. 10 a1g -0.02660220 H = -0.72388 eV Gap : +0.32442282 H = +8.82800 eV Number of MOs= 260, Electrons= 132.00, Symmetry: d3d xyz-coordinates of the MP2/TZVPP structure in Angstrom units P -1.6163530 0.9332018 -0.6228051 P -1.6163530 -0.9332018 0.6228051 P 0.0000000 -1.8664037 -0.6228051 P 1.6163530 -0.9332018 0.6228051 P 1.6163530 0.9332018 -0.6228051 P 0.0000000 1.8664037 0.6228051 I -3.4501425 1.9919407 0.6040284 I -3.4501425 -1.9919407 -0.6040284 I 0.0000000 3.9838813 -0.6040284 I 0.0000000 -3.9838813 0.6040284 I 3.4501425 1.9919407 0.6040284 I 3.4501425 -1.9919407 -0.6040284 # mode symmetry wave number IR intensity selection rules # cm**(-1) km/mol IR RAMAN 1 0.00 0.00000 - - 2 0.00 0.00000 - - 3 0.00 0.00000 - - 4 0.00 0.00000 - - 5 0.00 0.00000 - - 6 0.00 0.00000 - - 7 eu 20.01 0.06480 YES NO 8 eu 20.01 0.06480 YES NO 9 a1g 32.82 0.00000 NO YES 10 a2u 48.01 0.01832 YES NO 11 eg 51.11 0.00000 NO YES 12 eg 51.11 0.00000 NO YES 13 a1u 58.24 0.00000 NO NO 14 eu 60.33 0.00155 YES NO 15 eu 60.33 0.00155 YES NO 16 eg 81.57 0.00000 NO YES 17 eg 81.57 0.00000 NO YES 18 a1g 100.04 0.00000 NO YES 19 eg 130.04 0.00000 NO YES 20 eg 130.04 0.00000 NO YES 21 a2u 143.59 0.10751 YES NO 22 a2g 165.74 0.00000 NO NO 23 eu 171.37 8.05028 YES NO 24 eu 171.37 8.05028 YES NO 25 eg 357.87 0.00000 NO YES 26 eg 357.87 0.00000 NO YES 27 eu 359.96 25.93247 YES NO

81

28 eu 359.96 25.93247 YES NO 29 a1g 379.29 0.00000 NO YES 30 a2u 384.41 2.18609 YES NO 31 a1u 399.69 0.00000 NO NO 32 eg 425.43 0.00000 NO YES 33 eg 425.43 0.00000 NO YES 34 eu 464.22 0.16409 YES NO 35 eu 464.22 0.16409 YES NO 36 a1g 485.23 0.00000 NO YES your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 298.1 tend= 298.1 numt= 1 zero point vibrational energy ----------------------------- zpe= 29.16 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 298.15 0.1000000 20.88 16.21 24.80 -124.27 82.75 0.70265 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 298.15 0.1000000 0.2393285 0.2476428 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 243.2 tend= 243.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 29.17 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 243.15 0.1000000 20.37 15.90 21.15 -86.92 69.79 0.65279 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 243.15 0.1000000 0.2314255 0.2397398 your wishes are : ------------------ panf= 0.1000 pend= 0.1000 nump= 1 tanf= 193.2 tend= 193.2 numt= 1 zero point vibrational energy ----------------------------- zpe= 29.17 kJ/mol T p ln(qtrans) ln(qrot) ln(qvib) chem.pot. energy entropy (K) (MPa) (kJ/mol) (kJ/mol) (kJ/mol/K) 193.15 0.1000000 19.80 15.56 17.42 -55.58 58.49 0.59892 T P Cv Cp (K) (MPa) (kJ/mol-K) (kJ/mol-K) 193.15 0.1000000 0.2194067 0.2277210

82

The calculated chemical shifts and coupling constants at the MPW1PW91 level

J-Couplings

(Hz) Chemical

Shift [ppm] Isotropic Shielding

Tensor [ppm] MPW1PW91 MPW1PW91 MPW1PW91 J(PP) 6-311G(2df) 6-311G(2df) 6-311G(2df)

P5S3Br2+ Cis Iso7 P1-2 -508.8 P1 166.8 109

P1-3 162.0 P2 136.4 140 P1-6 54.8 P3 88.5 188 P1-8 -433.3 P6 245.6 31 P8 121.9 154 P2-3 -214.9 P2-6 85.6 P2-8 -53.8 P3-6 49.7 P3-8 -256.5 P6-8 44.1

J-Couplings

(Hz) Chemical

Shift [ppm] Isotropic Shielding

Tensor [ppm] MPW1PW91 MPW1PW91 MPW1PW91 J(PP) 6-311G(2df) 6-311G(2df) 6-311G(2df)

P4S4Br+ P1-2 228.6 P1 168.8 127 P1-3 -183.5 P2 190.4 106 P1-4 30.9 P3 113.8 182 P4 287.4 9 P2-3 -490.2 P2-4 32.7 P3-4 60.3

P4S5 P1-2 148.9 P1 117.3 184 P1-3 -220.0 P2 136.2 165 P1-4 12.4 P3 81.3 220 P4 241.8 59 P2-3 -364.3 P2-4 18.8 P3-4 47.0

83

J-Couplings

(Hz) Chemical

Shift [ppm] Isotropic Shielding

Tensor [ppm] MPW1PW91 MPW1PW91 MPW1PW91 J(PP) 6-311G(2df) 6-311G(2df) 6-311G(2df)

P5S2Br P1-2 -321.5 P1 199.6 124 P1-5 -463.3 P2 45.8 278 P1-3 -23.3 P3 -51.2 375 P1-4 3.3 P4 -75.9 400 P2-3 56.6 P5 -223.5 547 P2-4 63.4 P2-5 42.3 P3-4 -238.0 P3-5 -214.0 P4-5 -209.0

P5S2Br2+ P1-2 -525.8 P1 265.0 53 P1-5 -771.5 P2 22.4 296 P1-3 -45.0 P3 -34.6 353 P1-4 -45.0 P4 -33.9 352 P2-3 77.3 P5 -313.1 631 P2-4 77.1 P2-5 -26.2 P3-4 -212.3 P3-5 -195.1 P4-5 -195.0

Calculated NMR spectra of the other Isomers. The reference for the assignment of these chemical shifts was the chemical shift of P4S3, i.e. δ31P = 0 ppm equals to 324.3 ppm for the absolute isotropic shielding tensor.

J-Couplings

(Hz) Chemical Shift

[ppm] Isotropic Shielding

Tensor [ppm] MPW1PW91 MPW1PW91 MPW1PW91 J(PP) 6-311G(2df) 6-311G(2df) 6-311G(2df)

P5S3Br2+ P1-2 13.2 P1 144.3 180

P1-4 32.3 P2 129.8 194 P1-5 150.4 P4 9.2 315 P1-6 -903.4 P5 19.0 305 P6 -265.7 590 P2-4 92.0 P2-5 92.7 P2-6 -73.8 P4-5 -170.1 P4-6 -171.8 P5-6 -203.9

84

J-Couplings

(Hz) Chemical Shift

[ppm] Isotropic Shielding

Tensor [ppm] MPW1PW91 MPW1PW91 MPW1PW91 J(PP) 6-311G(2df) 6-311G(2df) 6-311G(2df)

P4S3PX2+_Iso1C1 P1-2 -380.5 P1 -80.1 404 P1-3 -26.1 P2 93.0 231 P1-6 89.8 P3 -99.0 423 P1-8 -43.5 P6 175.6 149 P8 240.8 84 P2-3 -400.8 P1 P2-6 30.6 P2 P2-8 -755.8 P3 P6 P3-6 90.2 P8 P3-8 -12.6 P6-8 2.1

J-Couplings

(Hz) Chemical Shift

[ppm] Isotropic Shielding

Tensor [ppm] MPW1PW91 MPW1PW91 MPW1PW91 J(PP) 6-311G(2df) 6-311G(2df) 6-311G(2df)

P4S3PX2+_Iso2C1 P1-2 -157.1 P1 -42.2 367 P1-3 -175.2 P2 -156.2 481

P1-6 88.6 P3 -61.9 386

P1-8 23.7 P6 115.3 209 P8 327.9 -4 P2-3 -140.5 P2-6 25.8 P2-8 -21.2 P3-6 93.4 P3-8 -2.2 P6-8

P4S3PX2+_Iso3C1 P1-2 -97.7 P1 -109.3 434

P1-3 -95.0 P2 -158.1 482 P1-5 17.7 P3 -109.4 434 P1-8 -16.7 P5 191.4 133 P8 222.2 102 P2-3 -97.7 P2-5 37.5 P2-8 45.9 P3-5 17.7 P3-8 -16.7 P5-8 -672.0

85