Journal of Physical Chemistry A, Vol.105, No.37, 8428-8433, 2001
Study of the perpendicular band intensities of the CH chromophore in CHCl3, CHBr3, and CHI3 with three-dimensional dipole moment surface from density functional calculations
The fundamental and overtone absolute intensities of the perpendicular band of the isolated CH chromophore in chloroform (CHCl3), bromoform (CHBr3), and iodoform (CHI3) have been calculated. The calculations were carried out by employing a three-dimensional curvilinear internal coordinate Hamiltonian and a polynomial expanded three-dimensional dipole moment surface (DMS). The DMS was obtained by a hybrid density functional method. Molecular symmetry was used to deduce the appropriate DMS expansion formulas. The calculated band intensities were compared with available experimental data. Most predicted values are accurate to within a factor of 2.