Far-infrared absorption spectra of water, ammonia, and chloroform calculated from instantaneous normal mode theory

Abstract

Instantaneous normal mode (INM) theory was used to calculate absolute far-infrared absorption spectra of water, ammonia, and chloroform. Three procedures for weighting the INM density of states to yield absorption intensities were tested against spectra based on dipole time correlation functions generated from molecular dynamics (MD) simulations. Weighting method I, which utilizes only the rotational character of a mode in determining its contribution to absorption, performed slightly better than method II, a more exact treatment which incorporates the extent to which a mode is IR-active. Method III, which includes the contributions of induced dipoles, was successful in describing the influence of induced dipoles on the far-infrared spectra of the model liquids. The contribution to absorption of unstable modes with imaginary frequencies was found to be significant at low frequencies, and was treated by a simple approximation. Agreement between INM theory and the MD analysis was quite good for chloroform and ammonia, but less so for water. Agreement with experimental data in the range of 4–100 cm−1 was generally poor, but no worse than that for the MD calculations, primarily reflecting the simple intermolecular potentials used rather than the computational method itself.