Time-Dependent Friction Effects on Vibrational Infrared Frequencies and Line Shapes of Liquid Water

From ab initio simulations of liquid water, the time dependent friction functions and time-averaged nonlinear effective bond potentials for the OH stretch and HOH bend vibrations are extracted. The obtained friction exhibits not only adiabatic contributions at and below the vibrational time scales but also much slower nonadiabatic contributions, reflecting homogeneous and inhomogeneous line broadening mechanisms, respectively. Intermolecular interactions in liquid water soften both stretch and bend potentials compared to the gas phase, which by itself would lead to a red-shift of the corresponding vibrational bands. In contrast, nonadiabatic friction contributions cause a spectral blue shift. For the stretch mode, the potential effect dominates, and thus, a significant red shift when going from gas to the liquid phase results. For the bend mode, potential and nonadiabatic friction effects are of comparable magnitude, so that a slight blue shift results, in agreement with well-known but puzzling experimental findings. The observed line broadening is shown to be roughly equally caused by adiabatic and nonadiabatic friction contributions for both the stretch and bend modes in liquid water. Thus, the quantitative analysis of the time-dependent friction that acts on vibrational modes in liquids advances the understanding of infrared vibrational frequencies and line shapes.

Automated summary

In this study, ab initio simulations were performed to investigate the friction functions and effective bond potentials for the OH stretch and HOH bend vibrations in liquid water. The results showed that intermolecular interactions resulted in the softening of the stretch and bend potentials, leading to a red-shift of the vibrational bands. However, nonadiabatic friction contributions caused a blue shift in the spectra. The observed line broadening in liquid water was found to be approximately equal due to adiabatic and nonadiabatic friction contributions for both the stretch and bend modes.