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Grupo de Espectroscopía Molecular, Lab. De Espectroscopia y Bioespectroscopia
Edificio Quifima, Unidad Asociada CSIC, Universidad de Valladolid
Valladolid, Spain
Cis-METHYL VINYL ETHER:
THE ROTATIONAL SPECTRUM UP TO 600 GHz
Lucie Kolesniková, Adam M. Daly, José L. Alonso
International Symposium on Molecular Spectroscopy, June 16 20, 2014Champaign-Urbana, Illinois, USA
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Gas-phase reactions leading from alcohols to ethersa
Introduction and motivation
a S.B. Charnley, M.E. Kress, A.G.G.M. Tielens, T.J. Millar, ApJ. 448 (1995)
CH3OH CH3OH2+ (CH3)2OH+ (CH3)2O
H3+, H3O+ CH3OH e-
HCO+
C2H5OH C2H5OH2+ (C2H5)2OH+ (C2H5)2O
HCO+e-
H3O+
CH3OC2H6+ CH3OC2H5
e-
C2H5OHCH3OH
C2H5OH
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Gas-phase reactions leading from alcohols to ethersa
Introduction and motivation
a S.B. Charnley, M.E. Kress, A.G.G.M. Tielens, T.J. Millar, ApJ. 448 (1995); b Z. Peeters, S.D. Rodgers, S.B. Charnley, L. Schriver-Mazzuoli, A.
Schriver, J.V. Keane, P. Ehrenfreund, A&A 445 (2006) 197-204; c Y.-J. Kuan, S.B. Charnley, T.L. Wilson, M. Ohishi, H.-C. Huang, L.E. Snyder,
Bull. Am. Astron. Soc. 31 (1999) 942; d G.W. Fuchs, U. Fuchs, T.F. Giesen, F. Wyrowski, A&A 444 (2005) 521–530.
CH3OH CH3OH2+ (CH3)2OH+ (CH3)2O
H3+, H3O+ CH3OH e-
HCO+
C2H5OH C2H5OH2+ (C2H5)2OH+ (C2H5)2O
HCO+e-
H3O+
CH3OC2H6+ CH3OC2H5
e-
C2H5OHCH3OH
C2H5OH
detectedb
tentativelydetectedc
detectedd
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Gas-phase reactions leading from alcohols to ethersa
CH3OH
Introduction and motivation
CH3OH2+ (CH3)2OH+ (CH3)2O
H3+, H3O+ CH3OH e-
HCO+
C2H5OH C2H5OH2+ (C2H5)2OH+ (C2H5)2O
HCO+e-
H3O+
CH3OC2H6+ CH3OC2H5
e-
C2H5OHCH3OH
C2H5OH
a S.B. Charnley, M.E. Kress, A.G.G.M. Tielens, T.J. Millar, ApJ. 448 (1995); b Z. Peeters, S.D. Rodgers, S.B. Charnley, L. Schriver-Mazzuoli, A.
Schriver, J.V. Keane, P. Ehrenfreund, A&A 445 (2006) 197-204; c Y.-J. Kuan, S.B. Charnley, T.L. Wilson, M. Ohishi, H.-C. Huang, L.E. Snyder,
Bull. Am. Astron. Soc. 31 (1999) 942; d G.W. Fuchs, U. Fuchs, T.F. Giesen, F. Wyrowski, A&A 444 (2005) 521–530; e B.E. Turner, A.J. Apponi, ApJ 561 (2001) L207-L210.
detectedb
tentativelydetectedc
detectedd
CH2CHOH detectede CH3OCHCH2 in the ISM ???
data only up to 40 GHz
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Experimental details
Double pass configuration (50 – 170 GHz)
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Experimental details
Double pass configuration (50 – 170 GHz)
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Experimental details
Double pass configuration (50 – 170 GHz)
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Experimental details
Double pass configuration (50 – 170 GHz)
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Experimental details
Double pass configuration (50 – 170 GHz)
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Experimental details
Single pass configuration (170 – 1000 GHz)
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Experimental details
Single pass configuration (170 – 1000 GHz)
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Experimental details
Single pass configuration (170 – 1000 GHz)
50 – 600 GHzroom temperature
20 mbar
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Rotational spectra and analysis
ma = 0.295 (2) D
mb = 0.910 (2) D
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Rotational spectra and analysis
ma = 0.295 (2) D
mb = 0.910 (2) D
n23 (A’’)
n24 (A’’)
n16 (A’)n24 234 cm1
n23 244 cm1
n16 327 cm1
a B. Cadioli, E. Gallinella, U. Pincelli, J. Mol. Struct. 78 (1982) 215 - 228.
Vib. modes below 400 cm1: a
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Rotational spectra and analysis
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Rotational spectra and analysis
ground statev24 = 1v23 = 1v16 = 1
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Rotational spectra and analysis
ncent (MHz)
Dn (MHz)
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Rotational spectra and analysisG.S.1 0
v24 = 11 0
v23 = 11 0
v16 = 11 0
ncent (MHz)
Dn (MHz)
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Rotational spectra and analysis
Ground state
> 2 800 transitions (J’’ = 69, Ka’’ = 25) Watson’s A-reduced Hamiltonian (Ir-representation)
v24 = 1 and v23 = 1 excited states
failure of the Watson’s semirigid Hamiltonian
IR dataa: DE = E23 E24 10.5 cm1
a B. Cadioli, E. Gallinella, U. Pincelli, J. Mol. Struct. 78 (1982) 215 - 228.
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Rotational spectra and analysis
Ered = E E24 J(J + 1)(B + C)/2
E red (
cm1
)ss
8
12
0, 1
1616
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Rotational spectra and analysis
Ered = E E24 J(J + 1)(B + C)/2
E red (
cm1
)ss
8
12
0, 1
1616
Ka = 0
0, 1
Ka = 0
0, 1
1, 2
8
5
2, 3
3, 4
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Rotational spectra and analysis
Ered = E E24 J(J + 1)(B + C)/2
E red (
cm1
)ss
8
12
0, 1
1616
Ka = 0
0, 1
Ka = 0
0, 1
1, 2
8
5
2, 3
3, 4
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Rotational spectra and analysis
v24 = 1 and v23 = 1 excited states
n23 (A’’)
n24 (A’’)
Cs symmetry
G(v24 = 1) G(v23 = 1) G(Jc) = A’
c-type Coriolis Fermi-type
HC(24,23) = iGcJc + Fab(JaJb + JbJa) + …
HF(24,23) = WF + WF
JJ2 + WFKJa
2 +W±(Jb2 – Jc
2) + …
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Rotational spectra and analysis
v24 = 1 and v23 = 1 excited states
> 1 200 transitions
J’’ = 61, Ka’’ = 10 for v24 = 1 and J’’ = 59, Ka’’ = 6 for v23 = 1
DE = 10.204550 (3) (cm1)
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Rotational spectra and analysis
v23 = 1, Ka = 1 v23 = 1, Ka = 0
v24 = 1, Ka = 2 v24 = 1, Ka = 3
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Rotational spectra and analysis
v24 = 1 and v23 = 1 excited states
V3 = 1256 cm–1 b
v23 = 1 state: higher Ka, Q-branches
transitions affected by the perturbations with v24 =
1 state
v24 = 1 state : only those affected by perturbations with v23 = 1 state
b R. Meyer, T.K. Ha, M. Oldani, W. Caminati, The Journal of Chemical Physics 86 (1987) 1848-1857.
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Rotational spectra and analysis
v24 = 1 and v23 = 1 excited states
V3 = 1256 cm–1 b
v23 = 1 state: higher Ka, Q-branches
perturbation induced splitting
v23 = 1, Ka = 0
v24 = 1, Ka = 3
v24 = 1, Ka = 3 ←2v23 = 1, Ka = 0 ← 1
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Rotational spectra and analysis
v24 = 1 and v23 = 1 excited states
V3 = 1256 cm–1 b
v23 = 1 state: higher Ka, Q-branches
perturbation induced splitting
v23 = 1, Ka = 0
v24 = 1, Ka = 3
v24 = 1, Ka = 3 ←2v23 = 1, Ka = 0 ← 1
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Rotational spectra and analysis
v16 = 1 excited state
isolated state
> 500 transitions (J’’ = 69, Ka’’ = 25)
A-reduction (Ir-representation)
n16 (A’)
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ResultsGround state v24 = 1 v23 = 1 v16 = 1
A (MHz) 18224.9674 (1) 18223.0348 (6) 18301.885 (3) 18395.7066 (9)B (MHz) 6388.99209 (3) 6359.0805 (1) 6330.9952 (5) 6365.8442 (2)C (MHz) 4875.85998 (3) 4875.1527 (1) 4855.6034 (1) 4854.33587 (9)DJ (kHz) 3.85336 (2) 3.8690 (1) 3.7446 (4) 3.8669 (1)DJK (kHz) –11.5212 (1) –11.502 (2) –10.112 (8) –13.760 (2)DK (kHz) 49.5624 (3) 49.165 (7) 49.74 (6) 56.44 (1)dJ (kHz) 1.183668 (7) 1.18187 (7) 1.1392 (2) 1.20168 (7)dK (kHz) 6.2388 (2) 5.240 (4) 4.69 (1) 8.540 (2)FJ (mHz) –1.138 (4) [–1.138] [–1.138] …FJK (mHz) 71.9 (1) [71.9] [71.9] 160 (1)FKJ (mHz) –450.0 (4) [–450.0] [–450.0] –790 (14)FK (mHz) 883.5 (5) [883.5] [883.5] 1300 (31)fJ (mHz) –0.243 (1) [–0.243] [–0.243] 0.208 (8)fJK (mHz) 10.58 (8) [10.58] [10.58]fK (mHz) 254 (1) [254] [254] 1321 (34)DE (MHz) 305924.7 (1)
(cm–1) 10.204550 (3)Gc (MHz) [1381]Gc
J (MHz) 0.00662 (1)Gc
K (MHz) –0.502 (1)Fab (MHz) –7.197 (4)Fab
K (MHz) –0.00275 (2)W± (MHz) 1.19453 (5)Gc
KK (MHz) 0.000077 (2)sfit (kHz) 32 58 32
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ResultsGround state v24 = 1 v23 = 1 v16 = 1
A (MHz) 18224.9674 (1) 18223.0348 (6) 18301.885 (3) 18395.7066 (9)B (MHz) 6388.99209 (3) 6359.0805 (1) 6330.9952 (5) 6365.8442 (2)C (MHz) 4875.85998 (3) 4875.1527 (1) 4855.6034 (1) 4854.33587 (9)DJ (kHz) 3.85336 (2) 3.8690 (1) 3.7446 (4) 3.8669 (1)DJK (kHz) –11.5212 (1) –11.502 (2) –10.112 (8) –13.760 (2)DK (kHz) 49.5624 (3) 49.165 (7) 49.74 (6) 56.44 (1)dJ (kHz) 1.183668 (7) 1.18187 (7) 1.1392 (2) 1.20168 (7)dK (kHz) 6.2388 (2) 5.240 (4) 4.69 (1) 8.540 (2)FJ (mHz) –1.138 (4) [–1.138] [–1.138] …FJK (mHz) 71.9 (1) [71.9] [71.9] 160 (1)FKJ (mHz) –450.0 (4) [–450.0] [–450.0] –790 (14)FK (mHz) 883.5 (5) [883.5] [883.5] 1300 (31)fJ (mHz) –0.243 (1) [–0.243] [–0.243] 0.208 (8)fJK (mHz) 10.58 (8) [10.58] [10.58]fK (mHz) 254 (1) [254] [254] 1321 (34)DE (MHz) 305924.7 (1)
(cm–1) 10.204550 (3)Gc (MHz) [1381]Gc
J (MHz) 0.00662 (1)Gc
K (MHz) –0.502 (1)Fab (MHz) –7.197 (4)Fab
K (MHz) –0.00275 (2)W± (MHz) 1.19453 (5)Gc
KK (MHz) 0.000077 (2)sfit (kHz) 32 58 32
New laboratory measurements
Precise spectroscopic constants
Search for cis-methyl vinyl ether in the ISM
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Acknowledgements
…and all the members of the
CSD 2009-00038Molecular Astrophysics
Grant VA070A08Grants CTQ 2010- 19008,
AYA 2009-07304 and AYA 2012-32032