title: First Principles Simulations of the Infrared Spectrum of Liquid Water Using Hybrid Density Functionals.
abstract: We show that first principles hybrid functional (PBE0) simulations of the infrared spectrum of liquid water yields a much better agreement with experimental results than a semilocal functional description; in particular, the quantitative accord with measured stretching and bending bands is very good. Such an improved description stems from two effects: a more accurate account, at the PBE0 level of theory, of the vibrational properties of the monomer and dimer and an underlying structural model for the liquid with a smaller number of hydrogen bonds and oxygen coordination than those obtained with semilocal functionals. The average electronic gap of the liquid is increased by 60% with respect to the PBE value, when computed at the PBE0 level of theory, and is in fair agreement with experimental results.
authors.affiliation: Department of Chemistry, University of California, Davis, California 95616, United States.
authors.forename: Cui
authors.initials: C
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, University of California, Davis, California 95616, United States.
authors.forename: Davide
authors.initials: D
authors.lastname: Donadio
authors.affiliation: Department of Applied Science, University of California, Davis, California 95616, United States.|Department of Computer Science, University of California, Davis, California 95616, United States.
authors.forename: François
authors.initials: F
authors.lastname: Gygi
authors.affiliation: Department of Chemistry, University of California, Davis, California 95616, United States.|Department of Physics, University of California, Davis, California 95616, United States.
authors.forename: Giulia
authors.initials: G
authors.lastname: Galli