Induction model for molecular electrostatics: application to the infrared spectroscopy of CO liquid.

ABSTRACT

Far-infrared intermolecular and midinfrared vibrational spectra of CO liquid have been calculated by Fourier transforming the quantum-corrected classical dipole correlation. The time dependence of the coordinates is determined from a standard nonpolarizable force field, and the dipole is determined from the coordinates with a "spectroscopic model" proposed herein. The model includes intramolecular induction and atomic charges, polarizabilities, and permanent dipoles. A good agreement with available experimental spectra is achieved. Our results demonstrate that the use of an anharmonic potential is necessary to reproduce the experimentally observed shift upon going from gas to liquid. The behavior of the simulated dipole time correlation functions suggests that CO liquid at 80 K exhibits aspects of both free rotation and solidlike caging. The proposition of some free rotation present in CO liquid supports Ewing's experimental hypothesis.