title: Efficient ab initio path integral hybrid Monte Carlo based on the fourth-order Trotter expansion: Application to fluoride ion-water cluster.
abstract: We propose an efficient path integral hybrid Monte Carlo (PIHMC) method based on fourth-order Trotter expansion. Here, the second-order effective force is employed to generate short trial trajectories to avoid computationally expensive Hessian matrix, while the final acceptance is judged based on fourth-order effective potential. The computational performance of our PIHMC scheme is compared with that of conventional PIHMC and PIMD methods based on second- and fourth-order Trotter expansions. Our method is applied to on-the-fly ab initio PIHMC calculation of fluoride ion-water complexes, F(-)(H(2)O) and F(-)(D(2)O), at ambient temperature, particularly focusing on the geometrical isotope effect.
authors.affiliation: Quantum Chemistry Division, Graduate School of Science, Yokohama City University, Seto 22-2, Kanazawa-ku, Yokohama 236-0027, Japan.
authors.forename: Kimichi
authors.initials: K
authors.lastname: Suzuki
authors.forename: Masanori
authors.initials: M
authors.lastname: Tachikawa
authors.forename: Motoyuki
authors.initials: M
authors.lastname: Shiga
mesh_terms: D005459:Fluorides / Q000737:chemistry*; D007477:Ions / Q000737:chemistry; D056004:Molecular Dynamics Simulation; D009010:Monte Carlo Method; D011789:Quantum Theory; D014867:Water / Q000737:chemistry*
chemical_list: D007477:Ions; D014867:Water; D005459:Fluorides