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

ABSTRACT: 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

SUBMITTER: Brunig FN 

PROVIDER: S-EPMC8883462 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature