Spectral diffusion in a fluctuating charge model of water.
We apply the combined electronic structure/molecular dynamics approach of Corcelli, Lawrence, and Skinner [J. Chem. Phys. 120, 8107 (2004)] to the fluctuating charge (SPC-FQ) model of liquid water developed by Rick, Stuart, and Berne [J. Chem. Phys. 101, 6141 (1994)]. For HOD in H(2)O the time scale for the long-time decay of the OD stretch frequency time-correlation function, which corresponds to the time scale for hydrogen-bond rearrangement in the liquid, is about 1.5 ps. This result is significantly longer than the 0.9 ps decay previously calculated for the nonpolarizable SPC/E water model. Our results for the SPC-FQ model are in better agreement with recent vibrational echo experiments.
Corcelli
S A
SA
Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.
Lawrence
C P
CP
Asbury
J B
JB
Steinel
T
T
Fayer
M D
MD
Skinner
J L
JL
D002627:Chemistry, Physical / Q000379:methods*; D003198:Computer Simulation; D017666:Deuterium Oxide / Q000737:chemistry; D004058:Diffusion; D004583:Electrons; D006860:Hydrogen Bonding; D008962:Models, Theoretical; D008968:Molecular Conformation; D013997:Time Factors; D014867:Water / Q000737:chemistry*
D014867:Water; D017666:Deuterium Oxide