CH-stretching overtone spectroscopy of 1,1,1,2-tetrafluoroethane.
We have recorded the vibrational absorption spectrum of 1,1,1,2-tetrafluoroethane (HFC-134a) in the fundamental and first five CH-stretching overtone regions with the use of Fourier transform infrared, dispersive long-path, intracavity laser photoacoustic, and cavity ringdown spectroscopies. We compare our measured total oscillator strengths in each region with intensities calculated using an anharmonic oscillator local mode model. We calculate intensities with 1D, 2D, and 3D Hamiltonians, including one or two CH stretches and two CH stretches with the HCH bending mode, respectively. The dipole moment function is calculated ab initio with self-consistent-field Hartree-Fock and density functional theories combined with double- and triple-zeta-quality basis sets. We find that the basis set choice affects the total intensity more than the choice of the Hamiltonian. We achieve agreement between the calculated and measured total intensities of approximately a factor of 2 or better for the fundamental and first five overtones.
Saar
Brian G
BG
Department of Chemistry, Williams College, Williamstown, Massachusetts 01267, USA.
Steeves
Adam H
AH
Thoman
John W
JW
Howard
Daryl L
DL
Schofield
Daniel P
DP
Kjaergaard
Henrik G
HG