Dipole Moment Derivatives and Infrared Intensities in Chloromethanes

摘要

The results of ab initio(MP2/6-31G) molecular orbital calculations of the dipole moment derivatives and gas phase IR intensities in chloromethanes are reported. The theoretical polar tensors are analyzed into the net charge, charge-flux, and overlap contributions. The charge-flux contribution was found to be dominant in the Cl atom polar tensor, while the net charge effect was the most prominent contribution for the H atom polar tensor. The Cl atom polar tensor appeared, in a good approximation, to be transferable among various chloro molecules. On the other hand, for the prediction of IR spectra of complex hydrocarbons containing chlorine atoms, some empirical adjustment of the H-atom polar tensor seemed to be made depending on the number of Cl atoms bound to the certain carbon atom.