Communications: On artificial frequency shifts in infrared spectra obtained from centroid molecular dynamics: Quantum liquid water.

Centroid molecular dynamics (CMD) is a popular method to extract approximate quantum dynamics from path integral simulations. Very recently we have shown that CMD gas phase infrared spectra exhibit significant artificial redshifts of stretching peaks, due to the so-called "curvature problem" imprinted by the effective centroid potential. Here we provide evidence that for condensed phases, and in particular for liquid water, CMD produces pronounced artificial redshifts for high-frequency vibrations such as the OH stretching band. This peculiar behavior intrinsic to the CMD method explains part of the unexpectedly large quantum redshifts of the stretching band of liquid water compared to classical frequencies, which is improved after applying a simple and rough "harmonic curvature correction."

[1]  D. Case,et al.  Quantum dynamical effects in liquid water: A semiclassical study on the diffusion and the infrared absorption spectrum. , 2009, The Journal of chemical physics.

[2]  B. Guillot,et al.  Quantum effects in simulated water by the Feynman–Hibbs approach , 1998 .

[3]  G. Schenter,et al.  A quantitative account of quantum effects in liquid water. , 2006, The Journal of chemical physics.

[4]  M. Karplus,et al.  Simulation of activation free energies in molecular systems , 1996 .

[5]  David E Manolopoulos,et al.  On the short-time limit of ring polymer molecular dynamics. , 2006, The Journal of chemical physics.

[6]  R. A. Kuharski,et al.  A quantum mechanical study of structure in liquid H2O and D2O , 1985 .

[7]  Lisandro Hernández de la Peña,et al.  Temperature dependence of quantum effects in liquid water. , 2005, Journal of the American Chemical Society.

[8]  Dominik Marx Prof..  Proton Transfer 200 Years after von Grotthuss: Insights from Ab Initio Simulations , 2007 .

[9]  P. Rossky,et al.  Feynman-Kleinert Linearized Path Integral (FK-LPI) Algorithms for Quantum Molecular Dynamics, with Application to Water and He(4). , 2006, Journal of chemical theory and computation.

[10]  Gregory A. Voth,et al.  Path‐Integral Centroid Methods in Quantum Statistical Mechanics and Dynamics , 2007 .

[11]  Ian R. Craig,et al.  Quantum statistics and classical mechanics: real time correlation functions from ring polymer molecular dynamics. , 2004, The Journal of chemical physics.

[12]  Alejandro Pérez,et al.  A comparative study of the centroid and ring-polymer molecular dynamics methods for approximating quantum time correlation functions from path integrals. , 2009, The Journal of chemical physics.

[13]  Dominik Marx,et al.  Proton transfer 200 years after von Grotthuss: insights from ab initio simulations. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[14]  Thomas E. Markland,et al.  Competing quantum effects in the dynamics of a flexible water model. , 2009, The Journal of chemical physics.

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

[16]  Gregory A Voth,et al.  The properties of water: insights from quantum simulations. , 2009, The journal of physical chemistry. B.

[17]  Wei Zhang,et al.  An accurate and simple quantum model for liquid water. , 2006, The Journal of chemical physics.

[18]  Peter J Rossky,et al.  Static and dynamic quantum effects in molecular liquids: a linearized path integral description of water. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[19]  K. Ando,et al.  Semiquantum molecular dynamics simulation of liquid water by time-dependent Hartree approach. , 2009, The Journal of chemical physics.

[20]  G. Voth,et al.  Infrared spectroscopy and hydrogen-bond dynamics of liquid water from centroid molecular dynamics with an ab initio-based force field. , 2009, The journal of physical chemistry. B.

[21]  Dominik Marx,et al.  On the applicability of centroid and ring polymer path integral molecular dynamics for vibrational spectroscopy. , 2009, The Journal of chemical physics.

[22]  Thomas F. Miller,et al.  Quantum diffusion in liquid water from ring polymer molecular dynamics. , 2005, The Journal of chemical physics.

[23]  J. Zinn-Justin.  Path integrals in quantum mechanics , 2005 .

[24]  H. Kleinert.  Path Integrals in Quantum Mechanics, Statistics, Polymer Physics, and Financial Markets , 2006 .

[25]  Nikos L. Doltsinis,et al.  Quantum Simulations of complex many-body systems:from theory to algorithms , 2002 .

[26]  David E Manolopoulos,et al.  Comparison of path integral molecular dynamics methods for the infrared absorption spectrum of liquid water. , 2008, The Journal of chemical physics.

[27]  P. Kusalik,et al.  Quantum effects in light and heavy liquid water: A rigid-body centroid molecular dynamics study. , 2004, The Journal of chemical physics.

[28]  F. Witte,et al.  Book Review: Path Integrals in Quantum Mechanics, Statistics, Polymer Physics and Financial Markets. Prof. Dr. Hagen Kleinert, 3rd extended edition, World Scientific Publishing, Singapore , 2003 .

[29]  Martin H. Müser,et al.  Path integral simulations of rotors: theory and applications , 1999 .

[30]  Gregory A. Voth,et al.  A quantum model for water: Equilibrium and dynamical properties , 1997 .