title: Collective solvent coordinates for the infrared spectrum of HOD in D2O based on an ab initio electrostatic map.
abstract: An ab initio MP2 vibrational Hamiltonian of HOD in an external electrostatic potential parametrized by the electric field and its gradient-tensor is constructed. By combining it with the fluctuating electric field induced by the D(2)O solvent obtained from molecular dynamics simulations, we calculate the infrared absorption of the O-H stretch. The resulting solvent shift and infrared line shape for three force fields (TIP4P, SPC/E, and SW) are in good agreement with the experiment. A collective coordinate response for the solvent effect is constructed by identifying the main electrostatic field and gradient components contributing to the line shape. This allows a realistic stochastic Liouville equation simulation of the line shapes which is not restricted to Gaussian frequency fluctuations.
authors.affiliation: Department of Chemistry, University of California, Irvine, California 92697-2025, USA.
authors.forename: Tomoyuki
authors.initials: T
authors.lastname: Hayashi
authors.forename: Thomas
authors.initials: T
authors.lastname: la Cour Jansen
authors.forename: Wei
authors.initials: W
authors.lastname: Zhuang
authors.forename: Shaul
authors.initials: S
authors.lastname: Mukamel
mesh_terms: D003198:Computer Simulation; D003903:Deuterium / Q000737:chemistry*; D004583:Electrons; D006859:Hydrogen / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry; D012997:Solvents / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D055672:Static Electricity; D014732:Vibration; D014867:Water / Q000737:chemistry*
chemical_list: D012997:Solvents; D014867:Water; D006859:Hydrogen; D003903:Deuterium; D010100:Oxygen