Infrared spectral profiles in liquids and atom-diatom interactions.

Molecular dynamics simulations of the infrared spectrum of a generic simple polar diatomic in a liquid nonpolar solvent allow to reproduce the different prototypical experimental line shapes of this kind of systems. This is feasible by using different solute-solvent anisotropic potentials at fixed thermodynamic conditions. In the limit cases, the rotation of the diatomic is explained in terms of a quasifree motion or a rotational diffusion evolution and the spectra show a doublet structure formed by P and R branches or a unique collapsed branch, respectively. When the profile contains three branches, including an intense Q branch in the vicinity of the center of the band, rotational evolution presents a particular hindering that can be understood by studying the influence on rotational spectral densities of the different time scales involved in rotational relaxation. Cancellation/enhancement effects among spectral density terms arising from intermediate and long times (0.4-1 ps) are essential to understand rotational hindering. (c) 2004 American Institute of Physics