Cooperation and Environment Characterize the Low-Lying Optical Spectrum of Liquid Water

Sudheer P. Kumar, Alessandro Genova, Michele Pavanello

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

The optical spectrum of liquid water is analyzed by subsystem time-dependent density functional theory. We provide simple explanations for several important (and so far elusive) features. Due to the disordered environment surrounding each water molecule, the joint density of states of the liquid is much broader than that of the vapor, thus explaining the red-shifted Urbach tail of the liquid compared to the gas phase. Confinement effects provided by the first solvation shell are responsible for the blue shift of the first absorption peak compared to the vapor. In addition, we also characterize many-body excitonic effects. These dramatically affect the spectral weights at low frequencies, contributing to the refractive index by a small but significant amount.

Original languageEnglish (US)
Pages (from-to)5077-5083
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume8
Issue number20
DOIs
StatePublished - Oct 19 2017

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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