Journal of Chemical Physics, Vol.112, No.17, 7484-7489, 2000
The ab initio calculated dipole moment surface and overtone relative intensities of CH chromophore in CHCl3
Relative absorption intensities of the Fermi resonance polyads of isolated CH chromophore for the CHCl3 molecule were calculated with one-dimensional and two-dimensional dipole moment surfaces, which are obtained by the ab initio density functional method. The calculation showed an unusual strong absorption at the second Fermi resonance polyad, which agrees well with the experimental data. Such an intensities anomaly can be attributed to the nonlinearity of the dipole moment surface in the vicinity of the equilibrium configuration. By taking advantage of the two-dimensional dipole moment surface where both CH stretching and bending vibrations are taken into consideration, the nu(1) and 2 nu(4) bands which constitute the first Fermi resonance polyad and have little wave function mixture, are found to be of almost equal intensity. Such a calculation agrees with observations.