High-resolution synchrotron FTIR spectroscopic analysis of the Coriolis interaction between the v10 = 1 and v8 = 1 states of ethylene-cis-1,2-d2

L L Ng, T L Tan, Andy Wong, Dominique R T Appadoo, Don McNaughton

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The synchrotron Fourier transform infrared (FTIR) spectrum of the b-type ν10 band of ethylene-cis-1,2-d2 (cis-C2H2D2) was recorded at a resolution of 0.00096 cm−1 in the 550–750 cm−1 region. The measured FWHM of the lines was about 0.002 cm 1. The ν10 band, centred at 662.871885(27) cm−1 was found to be perturbed through a b-type Coriolis resonance with the infrared inactive ν8 at 759.9582(20) cm−1. In this work, 1989 infrared transitions of ν10 were assigned for the first time. These perturbed and unperturbed infrared transitions were fitted with an rms deviation of 0.00033 cm−1 using the Watson's A-reduced Hamiltonian in the Ir representation with three Coriolis terms to derive the rovibrational constants for v10 = 1 and v8 = 1 states. Ground state rovibrational constants up to two sextic terms were also derived from a fit of a total of 2532 ground state combination differences with arms deviation of 0.00030 cm−1 from the infrared transitions of the present analysis and those determined previously. The ground state constants compared favourably to the equilibrium state constants from harmonic cc-pVTZ basis set at CCSD(T), MP2 and B3LYP levels. The rotational constants of ν10 and ν8 from this work agree well with those from anharmonic calculations.

Original languageEnglish
Pages (from-to)2798-2807
Number of pages10
JournalMolecular Physics
Volume114
Issue number19
DOIs
Publication statusPublished - 1 Oct 2016

Keywords

  • cis-CHD
  • ethylene isotopologue
  • Ethylene-cis-1,2-d
  • high-resolution FTIR spectroscopy
  • rovibrational constants

Cite this

@article{1cc0ad140fd34f6baffcff2addad0067,
title = "High-resolution synchrotron FTIR spectroscopic analysis of the Coriolis interaction between the v10 = 1 and v8 = 1 states of ethylene-cis-1,2-d2",
abstract = "The synchrotron Fourier transform infrared (FTIR) spectrum of the b-type ν10 band of ethylene-cis-1,2-d2 (cis-C2H2D2) was recorded at a resolution of 0.00096 cm−1 in the 550–750 cm−1 region. The measured FWHM of the lines was about 0.002 cm− 1. The ν10 band, centred at 662.871885(27) cm−1 was found to be perturbed through a b-type Coriolis resonance with the infrared inactive ν8 at 759.9582(20) cm−1. In this work, 1989 infrared transitions of ν10 were assigned for the first time. These perturbed and unperturbed infrared transitions were fitted with an rms deviation of 0.00033 cm−1 using the Watson's A-reduced Hamiltonian in the Ir representation with three Coriolis terms to derive the rovibrational constants for v10 = 1 and v8 = 1 states. Ground state rovibrational constants up to two sextic terms were also derived from a fit of a total of 2532 ground state combination differences with arms deviation of 0.00030 cm−1 from the infrared transitions of the present analysis and those determined previously. The ground state constants compared favourably to the equilibrium state constants from harmonic cc-pVTZ basis set at CCSD(T), MP2 and B3LYP levels. The rotational constants of ν10 and ν8 from this work agree well with those from anharmonic calculations.",
keywords = "cis-CHD, ethylene isotopologue, Ethylene-cis-1,2-d, high-resolution FTIR spectroscopy, rovibrational constants",
author = "Ng, {L L} and Tan, {T L} and Andy Wong and Appadoo, {Dominique R T} and Don McNaughton",
year = "2016",
month = "10",
day = "1",
doi = "10.1080/00268976.2016.1184341",
language = "English",
volume = "114",
pages = "2798--2807",
journal = "Molecular Physics",
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High-resolution synchrotron FTIR spectroscopic analysis of the Coriolis interaction between the v10 = 1 and v8 = 1 states of ethylene-cis-1,2-d2. / Ng, L L; Tan, T L; Wong, Andy; Appadoo, Dominique R T; McNaughton, Don.

In: Molecular Physics, Vol. 114, No. 19, 01.10.2016, p. 2798-2807.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - High-resolution synchrotron FTIR spectroscopic analysis of the Coriolis interaction between the v10 = 1 and v8 = 1 states of ethylene-cis-1,2-d2

AU - Ng, L L

AU - Tan, T L

AU - Wong, Andy

AU - Appadoo, Dominique R T

AU - McNaughton, Don

PY - 2016/10/1

Y1 - 2016/10/1

N2 - The synchrotron Fourier transform infrared (FTIR) spectrum of the b-type ν10 band of ethylene-cis-1,2-d2 (cis-C2H2D2) was recorded at a resolution of 0.00096 cm−1 in the 550–750 cm−1 region. The measured FWHM of the lines was about 0.002 cm− 1. The ν10 band, centred at 662.871885(27) cm−1 was found to be perturbed through a b-type Coriolis resonance with the infrared inactive ν8 at 759.9582(20) cm−1. In this work, 1989 infrared transitions of ν10 were assigned for the first time. These perturbed and unperturbed infrared transitions were fitted with an rms deviation of 0.00033 cm−1 using the Watson's A-reduced Hamiltonian in the Ir representation with three Coriolis terms to derive the rovibrational constants for v10 = 1 and v8 = 1 states. Ground state rovibrational constants up to two sextic terms were also derived from a fit of a total of 2532 ground state combination differences with arms deviation of 0.00030 cm−1 from the infrared transitions of the present analysis and those determined previously. The ground state constants compared favourably to the equilibrium state constants from harmonic cc-pVTZ basis set at CCSD(T), MP2 and B3LYP levels. The rotational constants of ν10 and ν8 from this work agree well with those from anharmonic calculations.

AB - The synchrotron Fourier transform infrared (FTIR) spectrum of the b-type ν10 band of ethylene-cis-1,2-d2 (cis-C2H2D2) was recorded at a resolution of 0.00096 cm−1 in the 550–750 cm−1 region. The measured FWHM of the lines was about 0.002 cm− 1. The ν10 band, centred at 662.871885(27) cm−1 was found to be perturbed through a b-type Coriolis resonance with the infrared inactive ν8 at 759.9582(20) cm−1. In this work, 1989 infrared transitions of ν10 were assigned for the first time. These perturbed and unperturbed infrared transitions were fitted with an rms deviation of 0.00033 cm−1 using the Watson's A-reduced Hamiltonian in the Ir representation with three Coriolis terms to derive the rovibrational constants for v10 = 1 and v8 = 1 states. Ground state rovibrational constants up to two sextic terms were also derived from a fit of a total of 2532 ground state combination differences with arms deviation of 0.00030 cm−1 from the infrared transitions of the present analysis and those determined previously. The ground state constants compared favourably to the equilibrium state constants from harmonic cc-pVTZ basis set at CCSD(T), MP2 and B3LYP levels. The rotational constants of ν10 and ν8 from this work agree well with those from anharmonic calculations.

KW - cis-CHD

KW - ethylene isotopologue

KW - Ethylene-cis-1,2-d

KW - high-resolution FTIR spectroscopy

KW - rovibrational constants

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U2 - 10.1080/00268976.2016.1184341

DO - 10.1080/00268976.2016.1184341

M3 - Article

VL - 114

SP - 2798

EP - 2807

JO - Molecular Physics

JF - Molecular Physics

SN - 0026-8976

IS - 19

ER -