HIGH RESOLUTION SPECTROSCOPY OF THE TWO LOWEST VIBRATIONAL STATES OF QUINOLINE C 9 H 7 N O. PIRALI,...
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Transcript of HIGH RESOLUTION SPECTROSCOPY OF THE TWO LOWEST VIBRATIONAL STATES OF QUINOLINE C 9 H 7 N O. PIRALI,...
HIGH RESOLUTION SPECTROSCOPY OF THE TWO LOWEST VIBRATIONAL STATES OF QUINOLINE C9H7N
O. PIRALI, Z. KISIEL, M. GOUBET, S. GRUET, M.-A. MARTIN-DRUMEL, A. CUISSET, F. HINDLE, G. MOURET
Institut des Sciences Moléculaires d’Orsay, CNRS-Université Paris-Sud
AILES beamline, synchrotron SOLEIL
Institute of Physics, Polish Academy of Sciences, Warszawa, Poland;
Laboratoire PhLAM, Université de Lille 1, Villeneuve de Ascq, France
Laboratoire de Physico-Chimie de l’Atmosphère, Université du Littoral Côte d’Opale, Dunkerque, France.
Low energy vibrational states of quinoline
GS A’
44 A’’ (178 cm-1)
45 A’’ (168 cm-1)
Prolate asymmetric topµa=0.2 D and µb=2.1 D45 vibrational modes (31 A’ and 14 A’’)
GS constants from Kisiel et al., JMS, 217 (2003)
0
170
cm-1
245 (338 cm-1)
244 (355 cm-1)45 + 44 (347 cm-1) 43 (392 cm-1)
43 (378 cm-1)350
FT-FIR spectroscopy (SOLEIL) : 45 – GS band
P branch R branch
- Spectral resolution = 30 MHz
- Determination of E45
- Rough values of A, B, C ES constants
- E45 - E44 separation
Sub-mm spectroscopy (LPCA+Warsaw):
- 140-220 GHz spectral range- 30 kHz line accuracy- b-type pure rotation in the GS, 45, 44
- Interstates transitions
- GS transitions- 45 transitions- 44 transitions
FTMW spectroscopy (PhLAM): ES transitions in the jet
45
44
Spherical moving mirror
MW Radiation
Gas injection
L-shaped antenna Vacuum : ≈ 10-6 mbar
Step by step motor
Stainless steel cell
Spherical mirror(Aluminum)
Pumping group
Pulsed nozzle
Gaussian beam profileW0= 42 mm à 12 GHz
1200 mm
Supersonic Jet
About 55 b-type transitions within 45 and 44
ES transitions are 1000 less intense than the corresponding GS transitions
25 GS a-type transitions
Frequency accuracy better than 2 kHz
Spectral analysis and identification of several perturbations
Use of AABS, LWW, and SPFIT/SPCAT softwares to analyse all the data
- 2 clear series of interacting levels with Ka=2- Other pertubed levels with unidentified perturbing partner
45 44
𝐻𝑟𝑜𝑡 =[𝐴− 12 (𝐵+𝐶 )] �̂� 𝑧2+(𝐵+𝐶 ) �̂� 2+ 1
2(𝐵−𝐶 ) ( �̂�𝑥2− �̂� 𝑦
2 )
− 𝐽 �̂�4− 𝐽𝐾 �̂�
2 �̂� 𝑧2−𝐾 �̂� 𝑧
4−𝐾 [ �̂� 𝑧2 , �̂� 𝑥2− �̂� 𝑦2 ]+¿−2 𝐽 �̂�
2 ( �̂� 𝑥2− �̂� 𝑦2 )¿
( 𝐻𝑟𝑜𝑡 𝐻𝑐𝑜𝑟
(45,44)+𝐻 𝐹(45,44 )
𝐻 𝑐𝑜𝑟(45,44 )+𝐻 𝐹
(45,44) 𝐻𝑟𝑜𝑡 +𝐸(45−44))
𝐻𝑐𝑜𝑟(45,44)=𝑖 (𝐺𝑐+𝐺𝑐
𝐽 𝑃2+𝐺𝑐𝐾 𝑃𝑧
2+… )𝑃 𝑦+(𝐹 𝑎𝑏+…)(𝑃𝑧𝑃 𝑥+𝑃𝑥𝑃 𝑧)
H F(45,44)=W F+W F
J P2+W FK P z
2+¿+[ (𝑊 ±+𝑊 ±
𝐽𝑃2+𝑊 ±𝐾 𝑃 𝑍
2 ) ,𝑃 𝑥𝑦2 ]+¿+… ¿
Hamiltonian : Watson A reduction and Ir representation
45
E45 5049310.(47)A 3141.723(10)B 1271.9959(11)C 906.4587(11)J 0.0191541(71)JK 0.056545(79)K 0.08473(12)J 0.00596471(64)K 0.0593138(77)
44
E44-E45 277935.(94)A 3142.092(10)B 1271.6425(11)C 906.4012(11)J 0.0192330(70)JK 0.037301(79)K 0.23231(12)J 0.00535848(62)K 0.0609730(72)
Results of the fit for 45 and 44
45/44
Gc 107.701(37)GcJ ‐0.0003270(16)GcK ‐0.001388(13)Fab [ 0.]Wf 22652.(288)WfJ ‐0.5218(19)WfK 5.5069(26)W [ 0.]WJ [ 0.]WK ‐0.000003605(29)
GS
A 3145.533086(71)B 1271.578056(61)C 905.739457(38)J 0.0191129(28)JK 0.0470270(89)K 0.161469(18)J 0.0056627(13)K 0.060613(22)
Lines RMS RMS error J’’ range Ka’’ range
GS 258 0.028 MHz 0.95 1-143 0-5845 3012 0.048 MHz 0.81 2-148 0-5844 2999 0.048 MHz 0.81 1-130 0-58
45 - GS 3578 0.0002 cm-1 1.02 9-114 9-60
E45 – EGS 5047475.91(13)E44 – E45 281603.51(13)
A 3141.723(10)B 1271.9959(11)C 906.4587(11)
Intercorrelation between parameters
ES rotational parameters
A 3142.092(10)B 1271.6425(11)C 906.4012(11)
Fermi parameter and vibrational energies
45
44
(𝐸 45 𝑊 𝐹𝑊 𝐹 𝐸 44−𝐸45)
(A1+A2)/2 3141.907426(29)(B1+B2)/2 1271.819307(15)(C1+C2)/2 906.429956(13)
(A1-A2)/2 ‐0.188(10)(B1-B2)/2 0.1771(10)(C1-C2)/2 0.0292(11)
45 5049310.(47)44 – 45 277935.(94)WF 22652.(288)
Conclusions
Use of very complementary techniques to study the rotational structure of GS, 45, and 44
Observation of perturbations in the rotational levels of 45 and 44
Similar difficulties might be encountered in the IR spectra of many PAHs molecules
Seems difficult to detect in the c-type transitions recorded by FTIR techniques
Analysis of the pure rotation transitions observed within the next vibrational polyad seems rather difficult
Acknowledgments
Beamtime allocation 20131274
ANR grant “GASPARIM”