Simultaneous analysis of the ν1, ν4, 2 ν2, ν2 + ν5, and 2 ν5 infrared bands of 12CH 3F

Abstract

The Fourier-transform spectrum of CH 3F from 2800 to 3100 cm −1, obtained by Guelachvili in Orsay at a resolution of about 0.003 cm −1, was analyzed. The effective Hamiltonian used contained all symmetry allowed interactions up to second order in the Amat-Nielsen classification, together with selected third-order terms, amongst the set of nine vibrational basis functions represented by the states ν 1( A 1), ν 4( E), 2 ν 2( A 1), ν 2 + ν 5( E), 2 ν 5 0( A 1), and 2 ν 5 ±2( E). A number of strong Fermi and Coriolis resonances are involved. The vibrational Hamiltonian matrix was not factorized beyond the requirements of symmetry. A total of 59 molecular parameters were refined in a simultaneous least-squares analysis to over 1500 upper-state energy levels for J ≤ 20 with a standard deviation of 0.013 cm −1. Although the standard deviation remains an order of magnitude greater than the precision of the measurements, this work breaks new ground in the simultaneous analysis of interacting symmetric top vibrational levels, in terms of the number of interacting vibrational states and the number of parameters in the Hamiltonian.