The Millimeter- and Submillimeter-Wave

Spectrum of Propenal

A. M. DALY, C. BERMÚDEZ, L. KOLESNIKOVÁ, AND J. L. ALONSO

Grupo de Espectroscopia MolecularLaboratorios de Espectroscopia y BioespectroscopiaEdificio Quifima. Parque CientíficoUniversidad de Valladolid SPAIN

ISMS 2014

Propenal

Acrolein

trans cis0 cm-1 600 cm-1

Simplest conjugated adlehyde

Sugar descomposition

Sugar descomposition

Amino acid formationMethionine Glutamic acidISMS

2014

Is propenal in the ISM?

Propanal[4]

6 lines 2 linesPropinal[4]

1 line

Sagitarius B2Green Bank18-26 GHz

ISMS 2014

Propenal[4]

[1] Sagdeev R.Z. et al. Nature 1986; [2] Matthews H.E. et al. ApJ 1985; [3]Hollis J.M.et al. ApJ 2000; [4]Hollis J.M. et al. ApJ 2004

Glycoaldehyde[3]

Acetaldehyde[2]

Formaldehyde[1]

Detection of propenal

Propenal2 lines

21 1 – 11 0

31 3 – 21 2

Sagitarius B2

Green Bank18-26 GHz

26079.449(1) MHz

18221.164(2) MHz

ISMS 2014

No more lines belonging to propenal have been detected in the ISM

[4]Hollis J.M. et al. ApJ 2004

1955[5]

1957[6]

1966[7]

1975[8]

1982[9]

1984[10]

ISMS 2014

Previous spectroscopy data

trans cis0 cm-1 600 cm-1

μa= 3.06(4)D[6]

μb= 0.54(14)D

μa= 2.010(5)D[9]

μb= 1.573(3)D

Rotational spectroscopy36 GHz, tgs, tν18

36 GHz, tgs, tν18, t2ν18, t3ν18

27 GHz, tgs, t1-9ν18, isotopologes 13C, 18O, D

50 GHz, cgs, cν18 180 GHz, tgs

Year

50 GHz, cgs, cν18 isotopologes 13C, 18O, D GHz measured

[5] Fine et al. JChemPhys. 1955; [6] Wagner R. et al. JChemPhys 1957; [7] Cherniak E.A. et al. JChemPhys 1966; [8] Winniwisser M. et al. Z. Naturforsch. 1975; [9] Bolm et al. ChemPhysL 1982; [10] Blom et al. JACS 1984

Previous spectroscopy data

trans cis0 cm-1 600 cm-1

μa= 3.06(4)D[6]

μb= 0.54(14)D

μa= 2.010(5)D[9]

μb= 1.573(3)D

ISMS 2014

High resolution Far-IR Spectroscopy[11]

tν18tν13

tν13+ tν18t3ν18

tν12tν17

t4ν18tν13+t2ν18

t2ν13

tgs t2ν18

[11] McKellar A.R.W. et al. JMolSpectrosc. 2008.

Our goals

ISMS 2014

Improving propenal rotational parameters

Facilitate the detection of more transitions belonging to propenal

ALMA project

Our goals

ISMS 2014

Improving propenal rotational parameters

trans

cis0 cm-1

600 cm-1

• Analyze the rotational spectrum of higher energy vibrational excited states• Extent the measurements of the vibrational excited states tgs and tν18

• Measurements at higher frequency range of the tgs isotopologues at natural abundance

• Analyze the rotational parameters of cgs at higher frequency ranges

Vibrational excited state energies

ISMS 2014

0

100

200

300

400

500

600

700

18+13(A')

17(A")12(A')

18+13(A")

13(A')

13(A')

G.S.(A')

18(A')

18(A")

18(A')

E/hc

(cm

-1)

18(A")

Interactions C-type Coriolis and Fermi

trans

Stark spectrometer frequency range has been extended up to ~110 GHz

Stark modulation spectroscopy

ISMS 2014

ISMS 2014

Stark modulation spectroscopy

34700 34800 34900 35000 35100 35200

Trans-propenal

tν18

tν13 tν18+ tν13 t3ν18tν12tν17

tν13+t2ν18t2ν13

tgs

t2ν18

34720 34740 34760 34780 34800 34820

t4ν18

41 4 – 31 3

tν13

tν12

tν17t2ν13

MMW and sub-MMW spectrum

• MMW and sub-MMW spectrometer (50 – 1000 GHz)

AM chains

Synthesizer

50-110 GHz, 135 – 480 GHz,500 – 700 GHz

room temperature

15 mTorr

Lock-in amplifier

Sample cellsDetector

ISMS 2014

RJ05 Lucie Kolesniková Medical Science Building 2:28pm

t3ν18

ISMS 2014

MMW and sub-MMW spectrum

tν13

t2ν18

tν13+ tν18

tgstν18

Δν (MHz)

ISMS 2014

MMW and sub-MMW spectrum

tν18

tgs

t2ν18

tν13

tν13+ tν18

t3ν18

Interactions

ISMS 2014

0

100

200

300

400

500

600

700

18+13(A')

17(A")12(A')

18+13(A")

13(A')

13(A')

G.S.(A')

18(A')

18(A")

18(A')

E/hc

(cm

-1)

18(A")

Gc/MHz -365.03(44 )Gc

J/MHz 0.00273(45 )Gc

K/MHz -0.2957(74 )Fab/MHz -4.676(73 )

W/MHz 82914.88(73 )W+-/MHz 0.09921(46 )W+-

J/MHz -4.77(188) ·10-6

W+-K/MHz 2.345(69) ·10-3

WJ/MHz -0.3067(208)WJK/MHz -2.655(50 ) ·10-3

WKK/MHz 0.5124(97 )

W/MHz 134543.7(102)W+-/MHz 0.2125(59 )W+-

J/MHz -0.143(46 ) ·10-6

WJ/MHz -0.5387(59 )WJK/MHz -2.964(177) ·10-3

WKK/MHz -41.45(138)

Fab/MHz 2.5449(50 )Gc/MHz 556.928(90 )Gc/MHz -0.00099(83 )

Gb/MHz -0.00657(42 )

Gb/MHz 0.03454(65 )Gb

K/MHz -0.000135(204)

E/MHz [157.1704856] [314.221907] [323.0193961] [468.94762] [482.826622]A/MHz 47353.68940(245) 45782.7002(100) 44391.655(141) 48738.976(140) 43110.34(97) 46941.35(89)B/MHz 4659.499457(87) 4666.24203(33) 4673.03078(136) 4659.19801(138) 4679.7384(80) 4665.1109(78)C/MHz 4242.689474(78) 4259.627077(290) 4276.62788(181) 4238.34635(179) 4293.4019(96) 4255.9631(93)ΔJ/kHz 1.0420990(300) 1.086567(95) 1.132468(159) 1.027465(157) 1.19007(40) 1.06501(34)ΔJK/kHz -8.78184(86) -8.53124(133) -8.2104(98) -10.3003(91) -7.681(42) -10.284(42)ΔK/kHz 358.149(149) -79.96(40) -331.2(49) 828.1(78) -255.9(162) 74.8(95)δJ/kHz 0.1202562(102) 0.118495(62) 0.116641(136) 0.118088(134) 0.116358(203) 0.112165(260)δK/kHz 5.7747(36) -0.6888(275) -6.237(62) 11.559(65) -6.536(131) 3.053(84)ΦJ/mHz 0.3142(39) 0.5668(141) 0.3803(120) 0.4040(124) 0.5938(161) 0.3101(191)ΦJK/mHz 8.62(164) 128.9(59) -251(149) -39.1(171) -88.7(178) 835.5(178)ΦKJ/mHz -507.4(62) 460.5(193) 2293(64) -1107(67) 3002(109) -2120(107)

ΦK/Hz -75.5(35) -555.8(60) [-75.5] 348.1(153) 4194(227) 5030(261)φJ/mHz 0.07667(159) 0.1066(78) -0.017(225) 0.0653(249) 0.2119(225) 0.193(32)φJK/mHz 8.78(85) 44.7(49) [8.78] [8.78] [8.78] [8.78]

φK/Hz 1.977(222) 16.56(79) -33.77(207) -2.45(248) 4.37(272) 133.9(315)LJJK/μHz 0.0532(244) -0.468(35)LJK/μHz -46.40(173) -162.81(160)LK/mHz 828(32) 2707.8(264)

Fitting

ISMS 2014

tν18tgs t2ν18

tν13tν13+ tν18

t3ν18

Nσ

8571,21398kHz

Alone 6 states fit Ref [8] Ref [11]

A/MHz 47353.7105(14) 45782.7002(100) 47353.7106 (44) 45783.0348 (87)B/MHz 4659.499489 (51) 4666.24203(33) 4659.49924 (19) 4666.24289 (96)C/MHz 4242.689471 (46) 4259.627077(290) 4242.68964 (19) 4259.6272 (10)ΔJ/kHz 1.042053 (16) 1.086567(95) 1.04153 (33) 1.086028 (93)ΔJK/kHz -8.78484(6) -8.53124(133) -8.78252 (28) -8.5460 (50)ΔK/kHz 360.421 (38) -79.96(40) 359.91 (46) -65.72 (21)δJ/kHz 0.1202785 (66) 0.118495(62) 0.119849 (84) 0.11831(67)δK/kHz 5.7400 (22) -0.6888(275) 5.7986 (22) -0.851(21)ΦJ/mHz 0.2960 (21) 0.5668(141) ... ΦJK/mHz -6.489 (39) 128.9(59) -12.3 (53)ΦKJ/mHz -509.6 (10) 460.5(193) -475.6 (93)

ΦK/Hz ... -555.8(60)φJ/mHz 0.07535 (96) 0.1066(78)φJK/mHz 3.43 (54) 44.7(49)

φK/Hz 16.56(79)LJJK/μHz -0.468(35)LJK/μHz -162.81(160)LK/mHz 2707.8(264)

Ground state trans

ISMS 2014

[8] Winniwisser M. et al. Z. Naturforsch. 1975; [11] McKellar A.R.W. et al. JMolSpectrosc. 2008

13C isotopologues

ISMS 2014

Cis isomer

ISMS 2014

Rotational parameters

ISMS 2014

tgs Trans 13C1 Trans 13C2 Trans 13C3cgs

A/MHz 47353.7105(14)a 47254.920(93) 46518.557(92) 46781.158(97) 22831.6481(43)

B/MHz 4659.499489(51) 4520.79373(27) 4642.43806(33) 4644.74078(37) 6241.04754(35)

C/MHz 4242.689471(46) 4126.64224(32) 4221.74680(32) 4225.83687(37) 4902.20752(21)

ΔJ/kHz 1.042053(16) 0.988653(90) 1.03242(13) 1.03950(14) 5.11348(24)

ΔJK/kHz -8.78484(38) -8.9420(15) -8.7379(15) -8.6746(34) -29.1849(12)

ΔK/kHz 360.421(53) 366.31(52) 320.7(10) 312.46(36) 108.03(12)

δJ/kHz 0.1202785(66) 0.111299(30) 0.121082(25) 0.120490(39) 1.48125(12)

δK/kHz 5.7400(22) 5.534(19) 5.556(13) 5.404(23) 11.3388(74)

ΦJ/mHz 0.2960(21) 0.228(15) 0.399(22) 0.171(26) 1.649(89)

ΦKJ/mHz -509.6(10) -399.7(80) -525.9(73) -413.(27) -1152.7(21)

ΦJK/mHz -6.489(39) [0.] [0.] [0.] 92.30(47)

φJ/mHz 0.07535(96) [0.] [0.] [0.] 1.111(43)

φJK/mHz 3.43(54) [0.] [0.] [0.] -18.6(20)

Nlinesc 1152,13 401,10 446,10 419,10 573,13

σfitc/kHz 29,9 42,2 44,5 42,1 38,7

321

ISMS 2014

Summary

• The spectrum of propenal has been measured up to 700GHz• Rotational parameters of the vibrational excited states below 600cm-1 has been obtained• The analysis of cgs tgs and its isotopologues has been updated up to 700MHz

Now it is time for you to find more lines of propenal in the interestllar medium

Acknowledgments

Grants CTQ 2010- 19008BES 2011-047685

CSD 2009-00038 Molecular Astrophysics

Grants VA070A08 and CIP13/01

Grupo de Espectroscopia Molecular (GEM) Laboratorios de Espectroscopia y

Bioespectroscopia, Unidad Asociada CSIC, UVa,Valladolid, Spain