Exploring the Absorption Spectrum of Simulated Water from MHz to the Infrared

Abstract

Absorption spectra of liquid water at 300 K are calculated from both classical and density functional theory molecular dynamics simulation data, which together span from 1 MHz to hundreds of THz, agreeing well with experimental data qualitativley and quantitavely over the entire range, including the IR modes, the microwave peak, and the intermediate THz bands. The spectra are decomposed into single-molecular and collective components as well as into components due to molecular reorientations and changes in induced intramolecular dipole moments. These decompositions shed new light on the motions underlying the librational and translational (hydrogen-bond stretch) bands at 20 and 5 THz respectively: interactions between donor protons and acceptor lone pair electrons are shown to be important for the line shape in both librational and translational regimes, and in- and out-of-phase librational dimer modes are observed and explored.

Main text: 7 pages with 4 figures. Supplement: 8 pages with 5 figures. Submitted to Nature Communications on February 29, 2020

References in corpus (2)

• Canonical sampling through velocity-rescaling
• Role of dipolar correlations in the IR spectra of water and ice

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