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Thermal quantum time-correlation functions from classical-like dynamics

Accepted version
Peer-reviewed

Type

Article

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Abstract

Thermal quantum time-correlation functions are of fundamental importance in quantum dynamics, allowing experimentally-measurable properties such as reaction rates, diffusion constants and vibrational spectra to be computed from first principles. Since the exact quantum solution scales exponentially with system size, there has been considerable effort in formulating reliable linear-scaling methods involving exact quantum statistics and approximate quantum dynamics modelled with classical-like trajectories. Here we review recent progress in the field with the development of methods including Centroid Molecular Dynamics (CMD), Ring Polymer Molecular Dynamics (RPMD) and Thermostatted RPMD (TRPMD). We show how these methods have recently been obtained from `Matsubara dynamics', a form of semiclassical dynamics which conserves the quantum Boltzmann distribution. We also rederive t->0+ quantum transition-state theory (QTST) in the Matsubara dynamics formalism showing that Matsubara-TST, like RPMD-TST, is equivalent to QTST. We end by surveying areas for future progress.

Description

Keywords

Correlation function, quantum dynamics, transition-state theory, ring polymers

Journal Title

Molecular Physics

Conference Name

Journal ISSN

0026-8976
1362-3028

Volume Title

115

Publisher

Informa UK Limited
Sponsorship
Timothy J. H. Hele wishes to thank Jesus College, Cambridge for a Research Fellowship.