A Laser-induced Fluorescence Spectroscopy Study of Rhodium MonosulfideRunhua Li and Walter J. Balfour

Department of Chemistry, University of VictoriaW. Scott Hopkins and Allan G. Adam

Department of Chemistry,University of New Brunswick

/nm Int. /nm Int. 552.82 m 503.54 s 551.30 s 503.42 ms 538.97 ms 501.82 mw 534.92 ms 492.22 mw 523.28 m 489.85 ms 519.78 s 488.96 mw 518.76 m 484.86 w 518.49 mw 483.80 w 514.64 mw 483.33 w 513.90 w 482.72 w 510.94 m 478.41 w 507.52 ms 472.99 w

Band heads observed in LIF spectra from Rh+CS2

s=strong; m=medium; w=weak

532 534 536 538 540 542 544 546 548 550 552 554 556

Laser-induced Fluorescence Spectrum of RhS

Wavelength/nm

=1/2

=3/2

43/241/2

538.

97 n

m

551.

30 n

m

552.

82 n

m

048

18130 (perturbed)

18550 cm-1

Observed electronic energy levels and transitions of RhS in LIF

RhS 18130 cm-1 band

18130 18131 18132 18133 18134 18135

876543210-1Q1(N)15

14

1617

109876543210R1(N) -1

cm-1

Partial High-Resolution Spectrum of 18130 cm-1 band for RhS

0 2 4 6 8 10 12 14 16 18-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0R

educ

ed te

rm v

alue

/ cm

-1

J

T-18130.28-0.14835J(J+1)±0.2228(J+1/2)

Reduced term value plot for the [18.13]1/2 state of RhS

Term Values (cm-1) in the 4- Ground State of RhS 4- ( =1/2 ) 4- ( =3/2 )

N F1 F2 F3 F4 -1 0 0 0.0986 0.7710 1 0.5197 1.6310 2 1.2534 2.8109 47.5353 3 2.3248 4.3185 48.3667 47.5389 4 3.7007 6.1425 49.5182 48.3686 5 5.4155 8.2901 51.0114 49.5240 6 7.4361 10.7544 52.8291 51.0136 7 9.7908 13.5415 54.9745 52.8366 8 12.4569 16.6744 57.4488 54.9840 9 15.4408 20.0654 60.2591 57.4718 10 18.7599 23.8228 63.3878 60.2825 11 22.3935 27.8734 66.8450 63.4217 12 26.3540 32.2684 70.6561 66.9083 13 30.6452 36.9695 74.7688 70.7039

Matrix of the Rotational Hamiltonian for a 4 Electronic State in a Case (a) Parity Basis

23 2

1

23

XXDXBX

DD

3)3(22/32

})]12(7[21

)]2/1(2[2)2/{(3

SD JX

JXDBX

21

Symmetric

)2/1](23)11(

21

)4(22)2/[(2)167(]47)4[(

)4(22/7)4(22

JX

XDBXXXD

XXB

SD

D

D

D

X=(J-1/2)(J+3/2). Upper and lower signs give the e (F1 and F3) and f (F2 and F4) levels respectively.

Fitted Ground State Parameters for RhSParameter Value/cm-1 Std. Devn.

B 0.163008 0.15×10-4

D 9×10-8 3×10-8

λ 11.857 1×10-3

λD 8.05×10-5 0.14×10-5

-0.0568 3×10-4

No. of data points = 463 ; Overall standard deviation = 0.0053 cm-1

0 1000 2000 3000 4000 5000 6000

1870

1415

950

475

A dispersed fluorescence spectrum of RhS

probe=538.995nm

Displacement/cm-1

5.3;485 """ eee x

Qualitative molecular orbital correlation diagram for RhS

A comparison of ground state data for some Rh diatomic species

Molecule RhN RhP RhO RhS RhF RhCl

Elect.Config 24 124 134

Symmetry 1 4

i3

B0 / cm-1 0.5075 0.204 0.4132 0.1630 0.2725 0.1279

r0 / nm 0.1642 0.186 0.1717 0.2059 0.1964 0.2275

G(1/2)/cm-1 897 507 797 475 575 340

Comparison of the molecular orbitals for the rhodium diatomics

Summary : Ground State of RhS

1

e

5-

8-

4

124

cminareparameters

5.3;485-0.0568(3)

108.05(14) ; 11.857(1)

109(3)D ; (15) 0.163008 B

)(:StateElectronic

:ionConfiguratElectron

ee

D

x

a

Rh

S

r0=0.2059 nm