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Details of Grant 

EPSRC Reference: EP/E01741X/1
Title: Quantum Effects in Molecular Dynamics
Principal Investigator: Manolopoulos, Professor D
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Department: Oxford Chemistry
Organisation: University of Oxford
Scheme: Standard Research
Starts: 01 October 2006 Ends: 31 March 2010 Value (£): 189,872
EPSRC Research Topic Classifications:
Gas & Solution Phase Reactions
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Summary on Grant Application Form
Most computer simulations of condensed phase systems assume that the nuclei move like classical particles, in accordance with Newton's equations of motion. In systems comprised of heavy atoms at high temperatures, this is usually quite a safe assumption. However, for systems containing hydrogen atoms under ambient conditions, quantum mechanical zero point energy and tunneling effects can be quite substantial. Indeed it is now well established that these effects are far from negligible in the dynamics of liquid water at room temperature. There is therefore considerable current interest in the incorporation of quantum mechanical effects in molecular dynamics simulations.In a series of recent papers, we have shown how the standard path integral molecular dynamics (PIMD) method, which has been used for the last twenty years to calculate the exact static equilibrium properties of quantum mechanical systems, can be generalized to calculate approximate real time quantum correlation functions, and so applied to the study of molecular dynamics. The resulting ring polymer molecular dynamics (RPMD) correlation functions are exact in several important limits, including the short-time limit, the classical limit, and the limit of a harmonic potential. They also satisfy the time-reversal and detailed-balance symmetries of the exact quantum mechanical correlation functions. The RPMD method provides a consistent (and often quite significant) improvement over purely classical molecular dynamics in a way that is routinely applicable to condensed phase simulations.So far, this method has been applied to the calculation of chemical reaction rates, to the diffusion in and the inelastic neutron scattering from a strongly quantum mechanical liquid (para-hydrogen), and to the translational and orientational diffusion in ambient liquid water, with highly encouraging results in all cases. The goal of the present proposal is to exploit this situation by using the method to investigate some questions of more general significance concerning the role of quantum mechanical effects in aqueous solvation dynamics and in the rates of proton transfer reactions in solution (see the project objectives for more details).
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