Grupo de Espectroscopía Molecular, Lab. De Espectroscopia y Bioespectroscopia Edificio Quifima, Unidad Asociada CSIC, Universidad de Valladolid Valladolid,

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

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



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+


HCO+e-

H3O+

CH3OC2H6+ CH3OC2H5

e-

C2H5OHCH3OH

C2H5OH

detectedb

tentativelydetectedc

detectedd


CH3OH


CH3OH2+ (CH3)2OH+ (CH3)2O

H3+, H3O+ CH3OH e-

HCO+


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

Experimental details

Double pass configuration (50 – 170 GHz)










Single pass configuration (170 – 1000 GHz)





50 – 600 GHzroom temperature

20 mbar

Rotational spectra and analysis

ma = 0.295 (2) D

mb = 0.910 (2) D


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



ground statev24 = 1v23 = 1v16 = 1


ncent (MHz)

Dn (MHz)

Rotational spectra and analysisG.S.1 0

v24 = 11 0

v23 = 11 0

v16 = 11 0

ncent (MHz)

Dn (MHz)


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.


Ered = E E24 J(J + 1)(B + C)/2

E red (

cm1

)ss

8

12

0, 1

1616


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


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



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) + …



> 1 200 transitions

J’’ = 61, Ka’’ = 10 for v24 = 1 and J’’ = 59, Ka’’ = 6 for v23 = 1

DE = 10.204550 (3) (cm1)


v23 = 1, Ka = 1 v23 = 1, Ka = 0

v24 = 1, Ka = 2 v24 = 1, Ka = 3



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.



V3 = 1256 cm–1 b


perturbation induced splitting

v23 = 1, Ka = 0

v24 = 1, Ka = 3

v24 = 1, Ka = 3 ←2v23 = 1, Ka = 0 ← 1



V3 = 1256 cm–1 b


perturbation induced splitting

v23 = 1, Ka = 0

v24 = 1, Ka = 3

v24 = 1, Ka = 3 ←2v23 = 1, Ka = 0 ← 1


v16 = 1 excited state

isolated state

> 500 transitions (J’’ = 69, Ka’’ = 25)

A-reduction (Ir-representation)

n16 (A’)

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

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

Acknowledgements

…and all the members of the

CSD 2009-00038Molecular Astrophysics

Grant VA070A08Grants CTQ 2010- 19008,

AYA 2009-07304 and AYA 2012-32032

Documents

Grupo de Espectroscopía Molecular, Lab. De Espectroscopia y Bioespectroscopia Edificio Quifima, Unidad Asociada CSIC, Universidad de Valladolid Valladolid,