Feynman-Kleinert Linearized Path Integral (FK-LPI) Algorithms for Quantum Molecular Dynamics, with Application to Water and He(4)

Jens Aage Poulsen; Gunnar Nyman; Peter J Rossky

doi:10.1021/ct600167s

Feynman-Kleinert Linearized Path Integral (FK-LPI) Algorithms for Quantum Molecular Dynamics, with Application to Water and He(4)

J Chem Theory Comput. 2006 Nov;2(6):1482-91. doi: 10.1021/ct600167s.

Authors

Jens Aage Poulsen¹, Gunnar Nyman¹, Peter J Rossky¹

Affiliation

¹ Physical Chemistry, Göteborg University, S-412-96, Göteborg, Sweden, and Institute for Theoretical Chemistry, Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712.

PMID: 26627018
DOI: 10.1021/ct600167s

Abstract

The Feynman-Kleinert Linearized Path Integral (FK-LPI) representation of quantum correlation functions is extended in applications and algorithms. Diffusion including quantum effects for a flexible simple point charge model of liquid water is explored, including new tests of internal consistency. An ab initio quantum correction factor (QCF) is also obtained to correct the far-infrared spectrum of water. After correction, a spectrum based on a classical simulation is in good agreement with the experiment. The FK-LPI QCF is shown to be superior to the so-called harmonic QCF. New computational algorithms are introduced so that the quantum Boltzmann Wigner phase-space density, the central object in the implementation, can be obtained for arbitrary potentials. One scheme requires only that the standard classical force routine be replaced when turning from one molecular problem to another. The new algorithms are applied to the calculation of the Van Hove spectrum of liquid He(4) at 27 K. The spectrum moments are in very good agreement with the experiment. These observations indicate that the FK-LPI approach can be broadly effective for molecular problems involving the dynamics of light nuclei.