title: Hydrogen Bonding and Related Properties in Liquid Water: A Car-Parrinello Molecular Dynamics Simulation Study.
abstract: The local hydrogen-bonding structure and dynamics of liquid water have been investigated using the Car-Parrinello molecular dynamics simulation technique. The radial distribution functions and coordination numbers around water molecules have been found to be strongly dependent on the number of hydrogen bonds formed by each molecule, revealing also the existence of local structural heterogeneities in the structure of the liquid. The results obtained have also revealed the strong effect of the local hydrogen-bonding network on the local tetrahedral structure and entropy. The investigation of the dynamics of the local hydrogen-bonding network in liquid water has shown that this network is very labile, and the hydrogen bonds break and reform very rapidly. Nevertheless, it has been found that the hydrogen-bonding states associated with the formation of four hydrogen bonds by a water molecule exhibit the largest survival probability and corresponding lifetime. The reorientational motions of water molecules have also been found to be strongly dependent on their initial hydrogen-bonding state. Finally, the dependence of the librational and vibrational modes of water molecules on the local hydrogen-bonding network has been carefully examined, revealing a significant effect upon the libration and bond-stretching peak frequencies. The calculated low frequency peaks come in agreement with previously reported interpretations of the experimental low-frequency Raman spectrum of liquid water.
authors.affiliation: †Departament de Física i Enginyeria Nuclear, Universitat Politecnica de Catalunya, Campus Nord B4-B5, Barcelona 08034, Spain.
authors.forename: Elvira
authors.initials: E
authors.lastname: Guardia
authors.affiliation: †Departament de Física i Enginyeria Nuclear, Universitat Politecnica de Catalunya, Campus Nord B4-B5, Barcelona 08034, Spain.|‡INAC/SPrAM (UMR 5819 UJF, CNRS, CEA), CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble, France.
authors.forename: Ioannis
authors.initials: I
authors.lastname: Skarmoutsos
authors.affiliation: §Dipartimento di Chimica e Farmacia, Universita degli Studi di Sassari, Istituto Officina dei Materiali del CNR, UOS SLACS, Via Vienna 2, 07100 Sassari, Italy.
authors.forename: Marco
authors.initials: M
authors.lastname: Masia
mesh_terms: D019277:Entropy; D006859:Hydrogen / Q000737:chemistry; D006860:Hydrogen Bonding; D056004:Molecular Dynamics Simulation; D010100:Oxygen / Q000737:chemistry; D013059:Spectrum Analysis, Raman; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water; D006859:Hydrogen; D010100:Oxygen