Fast centroid molecular dynamics: a force-matching approach for the predetermination of the effective centroid forces.

A fast centroid molecular dynamics (CMD) methodology is proposed in which the effective centroid forces are predetermined through a force-matching algorithm applied to a standard path integral molecular dynamics simulation. The resulting method greatly reduces the computational cost of generating centroid trajectories, thus extending the applicability of CMD. The method is applied to the study of liquid para-hydrogen at two state points and liquid ortho-deuterium at one state point. The static and dynamical results are compared to those obtained from full adiabatic CMD simulations and found to be in excellent agreement for all three systems; the transport properties are also compared to experiment and found to have a similar level of agreement.

[1]  N. Mermin,et al.  Determination of Thermodynamic Green's Functions , 1961 .

[2]  Nancy Makri,et al.  Influence functionals with semiclassical propagators in combined forward-backward time , 1999 .

[3]  Gregory A. Voth,et al.  Hyper-parallel algorithms for centroid molecular dynamics: application to liquid para-hydrogen , 1996 .

[4]  Y. Yonetani,et al.  Centroid molecular dynamics approach to the transport properties of liquid para-hydrogen over the wide temperature range. , 2004, The Journal of chemical physics.

[5]  K. Kinugawa.  Path integral centroid molecular dynamics study of the dynamic structure factors of liquid para-hydrogen , 1998 .

[6]  Victor V. Goldman,et al.  The isotropic intermolecular potential for H2 and D2 in the solid and gas phases , 1978 .

[7]  Jianshu Cao,et al.  The formulation of quantum statistical mechanics based on the Feynman path centroid density. III. Phase space formalism and analysis of centroid molecular dynamics , 1994 .

[8]  Gregory A. Voth,et al.  A derivation of centroid molecular dynamics and other approximate time evolution methods for path integral centroid variables , 1999 .

[9]  E. Rabani,et al.  A self-consistent mode-coupling theory for dynamical correlations in quantum liquids: Application to liquid para-hydrogen , 2002 .

[10]  Bermejo,et al.  Quantum effects on liquid dynamics as evidenced by the presence of well-defined collective excitations in liquid para-hydrogen , 2000, Physical Review Letters.

[11]  W. Miller,et al.  Forward-backward initial value representation for semiclassical time correlation functions , 1999 .

[12]  Pierre-Nicholas Roy,et al.  Connection between the observable and centroid structural properties of a quantum fluid: application to liquid para-hydrogen. , 2004, The Journal of chemical physics.

[13]  G. Martyna,et al.  Adiabatic path integral molecular dynamics methods. II. Algorithms , 1996 .

[14]  Jianshu Cao,et al.  The formulation of quantum statistical mechanics based on the Feynman path centroid density. IV. Algorithms for centroid molecular dynamics , 1994 .

[15]  Seogjoo J. Jang,et al.  Path integral centroid variables and the formulation of their exact real time dynamics , 1999 .

[16]  Jianshu Cao,et al.  The formulation of quantum statistical mechanics based on the Feynman path centroid density. II. Dynamical properties , 1994 .

[17]  Mark Jarrell,et al.  Bayesian inference and the analytic continuation of imaginary-time quantum Monte Carlo data , 1996 .

[18]  Gregory A Voth,et al.  Effective force fields for condensed phase systems from ab initio molecular dynamics simulation: a new method for force-matching. , 2004, The Journal of chemical physics.

[19]  G. Voth,et al.  Pseudopotentials for centroid molecular dynamics: Application to self-diffusion in liquid para-hydrogen , 1996 .

[20]  Eran Rabani,et al.  A fully self-consistent treatment of collective fluctuations in quantum liquids. , 2004, The Journal of chemical physics.

[21]  Y. Yonetani,et al.  Transport properties of liquid para-hydrogen: The path integral centroid molecular dynamics approach , 2003 .

[22]  Nancy Makri,et al.  Semiclassical influence functionals for quantum systems in anharmonic environments 1 Presented at th , 1998 .

[23]  K. Kinugawa,et al.  Molecular collective dynamics in solid para-hydrogen and ortho-deuterium: The Parrinello–Rahman-type path integral centroid molecular dynamics approach , 2003 .

[24]  F. Bermejo,et al.  Microscopic dynamics in liquid deuterium: A transition from collective to single-particle regimes , 1997 .

[25]  G. Voth,et al.  A centroid molecular dynamics study of liquid para-hydrogen and ortho-deuterium. , 2004, The Journal of chemical physics.

[26]  Jianshu Cao,et al.  A new perspective on quantum time correlation functions , 1993 .

[27]  R. Feynman,et al.  Quantum Mechanics and Path Integrals , 1965 .

[28]  S. Okazaki,et al.  A path integral centroid molecular dynamics study of nonsuperfluid liquid helium-4 , 1999 .

[29]  E. Rabani,et al.  Self-consistent mode-coupling theory for self-diffusion in quantum liquids. , 2001, Physical review letters.