Forward--backward semiclassical dynamics with information-guided noise reduction for a molecule in solution.
The forward--backward semiclassical dynamics (FBSD) methodology is used to obtain expressions for time correlation functions of a system (atom or molecule) in solution. We use information-guided noise reduction (IGNoR) [Makri, N. Chem. Phys. Lett. 2004, 400, 446] to minimize the statistical error associated with the Monte Carlo integration of oscillatory functions. This is possible by reformulating the correlation function in terms of an oscillatory solvent-dependent contribution whose integral can be obtained analytically and a slowly varying function obtained via a grid-based iterative evaluation of solute properties. Knowledge of the exact integral of the oscillatory function, combined with correlated statistics, leads to partial cancellation of the Monte Carlo error. Application on a one-dimensional solute-solvent model shows a substantial improvement of convergence in the IGNoR-enhanced FBSD correlation function for a fixed number of Monte Carlo samples. The reduction of statistical error achieved by using the IGNoR methodology becomes more significant as the number of solvent particles increases.
Department of Chemistry, University of Illinois, 601 South Goodwin Avenue, Urbana, Illinois 61801, USA.
Edward
E
Bukhman
Nancy
N
Makri