title: Ab initio path integral simulations for the fluoride ion-water clusters: competitive nuclear quantum effect between F(-)-water and water-water hydrogen bonds.
abstract: Small hydrated fluoride ion complexes, F(-)(H2O)n (n = 1-3), have been studied by ab initio hybrid Monte Carlo (HMC) and ab initio path integral hybrid Monte Carlo (PIHMC) simulations. Because of the quantum effect, our simulation shows that the average hydrogen-bonded F(-)···HO distance in the quantum F(-)(H2O) is shorter than that in the classical one, while the relation inverts at the three water molecular F(-)(H2O)3 cluster. In the case of F(-)(H2O)3, we have found that the nuclear quantum effect enhances the formation of hydrogen bonds between two water molecules. In F(-)(H2O)2 and F(-)(H2O)3, the nuclear quantum effect on two different kinds of hydrogen bonds, F(-)-water and water-water hydrogen bonds, competes against each other. In F(-)(H2O)3, thus, the nuclear quantum effect on the water-water hydrogen bond leads to the elongation of hydrogen-bonded F(-)···HO distance, which we suggest this as the possible origin of the structural inversion from F(-)(H2O) to F(-)(H2O)3.
authors.affiliation: Quantum Chemistry Division, Graduate School of Science, Graduate School of Nanobioscience, Yokohama City University , Yokohama 236-0027, Japan.
authors.forename: Yukio
authors.initials: Y
authors.lastname: Kawashima
authors.forename: Kimichi
authors.initials: K
authors.lastname: Suzuki
authors.forename: Masanori
authors.initials: M
authors.lastname: Tachikawa
mesh_terms: D005459:Fluorides / Q000737:chemistry*; D006860:Hydrogen Bonding; D007477:Ions / Q000737:chemistry; D009010:Monte Carlo Method; D011789:Quantum Theory; D014867:Water / Q000737:chemistry*
chemical_list: D007477:Ions; D014867:Water; D005459:Fluorides