The Millimeter- and Submillimeter-Wave Spectrum of Propenal A. M. DALY, C. BERMÚDEZ, L....
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![Page 1: The Millimeter- and Submillimeter-Wave Spectrum of Propenal A. M. DALY, C. BERMÚDEZ, L. KOLESNIKOVÁ, AND J. L. ALONSO Grupo de Espectroscopia Molecular.](https://reader035.fdocuments.us/reader035/viewer/2022062503/5a4d1aed7f8b9ab05997c361/html5/thumbnails/1.jpg)
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
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Propenal
Acrolein
trans cis0 cm-1 600 cm-1
Simplest conjugated adlehyde
Sugar descomposition
Sugar descomposition
Amino acid formationMethionine Glutamic acidISMS
2014
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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]
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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
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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
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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.
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Our goals
ISMS 2014
Improving propenal rotational parameters
Facilitate the detection of more transitions belonging to propenal
ALMA project
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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
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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
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Stark spectrometer frequency range has been extended up to ~110 GHz
Stark modulation spectroscopy
ISMS 2014
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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
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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
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t3ν18
ISMS 2014
MMW and sub-MMW spectrum
tν13
t2ν18
tν13+ tν18
tgstν18
Δν (MHz)
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ISMS 2014
MMW and sub-MMW spectrum
tν18
tgs
t2ν18
tν13
tν13+ tν18
t3ν18
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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)
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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
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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
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13C isotopologues
ISMS 2014
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Cis isomer
ISMS 2014
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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
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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
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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