Abstract
The infrared spectrum of the ν6 band of ethylene-cis-1,2-d2 (cis-C2H2D2) was recorded at the Australian Synchrotron in the 980–1100 cm−1 region at an unapodized resolution of 0.00096 cm−1. Some of the transitions of the ν6 band centered at 1039.768335(30) cm−1 were perturbed by the upper energy levels of the infrared inactive ν4 band at 980.364(24) cm−1 by an a-type Coriolis interaction. Rovibrational analysis of a total of 941 unperturbed and perturbed infrared transitions of the ν6 band was carried out using an asymmetric rotor fitting program based on the Watson's A-reduced Hamiltonian in the Ir representation to derive up to 2 sextic constants for the ν6 = 1 state and 3 rotational constants (A, B, and C) for the ν4 = 1 state with a rms deviation of 0.00028 cm−1. From the perturbed analysis, the a-type Coriolis resonance parameter Z6,4a for the ν6 and ν4 interacting bands was determined to be 0.5249(14) cm−1. The band center and the rotational constants of the ν6 = 1 state were found to agree within 1% to the calculated values using B3LYP/cc-pVTZ and MP2/cc-pVTZ levels of theory. Furthermore, the a-type Coriolis coupling constant of these two bands derived from this work were compared to those experimentally determined previously and presently calculated.
| Original language | English |
|---|---|
| Pages (from-to) | 8-12 |
| Number of pages | 5 |
| Journal | Journal of Molecular Spectroscopy |
| Volume | 329 |
| DOIs | |
| Publication status | Published - 1 Nov 2016 |
Keywords
- FTIR spectroscopy
- High-resolution FTIR spectrum of cis-CHD
- Rovibrational constants
- Synchrotron infrared spectrum
- ν band of ethylene-cis-1,2-d
Cite this
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The Coriolis-interacting ν6 and ν4 bands of ethylene-cis-1,2-d2 (cis-C2H2D2) by high-resolution synchrotron Fourier transform infrared (FTIR) spectroscopy. / Tan, T L; Gabona, M G; Wong, Andy; Appadoo, Dominique R T; McNaughton, Don.
In: Journal of Molecular Spectroscopy, Vol. 329, 01.11.2016, p. 8-12.Research output: Contribution to journal › Article › Research › peer-review
TY - JOUR
T1 - The Coriolis-interacting ν6 and ν4 bands of ethylene-cis-1,2-d2 (cis-C2H2D2) by high-resolution synchrotron Fourier transform infrared (FTIR) spectroscopy
AU - Tan, T L
AU - Gabona, M G
AU - Wong, Andy
AU - Appadoo, Dominique R T
AU - McNaughton, Don
PY - 2016/11/1
Y1 - 2016/11/1
N2 - The infrared spectrum of the ν6 band of ethylene-cis-1,2-d2 (cis-C2H2D2) was recorded at the Australian Synchrotron in the 980–1100 cm−1 region at an unapodized resolution of 0.00096 cm−1. Some of the transitions of the ν6 band centered at 1039.768335(30) cm−1 were perturbed by the upper energy levels of the infrared inactive ν4 band at 980.364(24) cm−1 by an a-type Coriolis interaction. Rovibrational analysis of a total of 941 unperturbed and perturbed infrared transitions of the ν6 band was carried out using an asymmetric rotor fitting program based on the Watson's A-reduced Hamiltonian in the Ir representation to derive up to 2 sextic constants for the ν6 = 1 state and 3 rotational constants (A, B, and C) for the ν4 = 1 state with a rms deviation of 0.00028 cm−1. From the perturbed analysis, the a-type Coriolis resonance parameter Z6,4a for the ν6 and ν4 interacting bands was determined to be 0.5249(14) cm−1. The band center and the rotational constants of the ν6 = 1 state were found to agree within 1% to the calculated values using B3LYP/cc-pVTZ and MP2/cc-pVTZ levels of theory. Furthermore, the a-type Coriolis coupling constant of these two bands derived from this work were compared to those experimentally determined previously and presently calculated.
AB - The infrared spectrum of the ν6 band of ethylene-cis-1,2-d2 (cis-C2H2D2) was recorded at the Australian Synchrotron in the 980–1100 cm−1 region at an unapodized resolution of 0.00096 cm−1. Some of the transitions of the ν6 band centered at 1039.768335(30) cm−1 were perturbed by the upper energy levels of the infrared inactive ν4 band at 980.364(24) cm−1 by an a-type Coriolis interaction. Rovibrational analysis of a total of 941 unperturbed and perturbed infrared transitions of the ν6 band was carried out using an asymmetric rotor fitting program based on the Watson's A-reduced Hamiltonian in the Ir representation to derive up to 2 sextic constants for the ν6 = 1 state and 3 rotational constants (A, B, and C) for the ν4 = 1 state with a rms deviation of 0.00028 cm−1. From the perturbed analysis, the a-type Coriolis resonance parameter Z6,4a for the ν6 and ν4 interacting bands was determined to be 0.5249(14) cm−1. The band center and the rotational constants of the ν6 = 1 state were found to agree within 1% to the calculated values using B3LYP/cc-pVTZ and MP2/cc-pVTZ levels of theory. Furthermore, the a-type Coriolis coupling constant of these two bands derived from this work were compared to those experimentally determined previously and presently calculated.
KW - FTIR spectroscopy
KW - High-resolution FTIR spectrum of cis-CHD
KW - Rovibrational constants
KW - Synchrotron infrared spectrum
KW - ν band of ethylene-cis-1,2-d
UR - http://www.scopus.com/inward/record.url?scp=84989329113&partnerID=8YFLogxK
U2 - 10.1016/j.jms.2016.08.018
DO - 10.1016/j.jms.2016.08.018
M3 - Article
VL - 329
SP - 8
EP - 12
JO - Journal of Molecular Spectroscopy
JF - Journal of Molecular Spectroscopy
SN - 0022-2852
ER -