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Nonadiabatic dynamics with quantum nuclei: Simulating charge transfer with ring polymer surface hopping

Ghosh, S; Giannini, S; Lively, K; Blumberger, J; (2019) Nonadiabatic dynamics with quantum nuclei: Simulating charge transfer with ring polymer surface hopping. Faraday Discussions 10.1039/c9fd00046a. (In press).

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Abstract

Investigation of many electronic processes in molecules and materials, such as charge and exciton transport, require a computational framework that incorporates both non-adiabatic electronic effects and nuclear quantum effects, in particular at low temperatures. We have recently developed an efficient semi-empirical fewest switches surface hopping method, denoted fragmentorbital based surface hopping (FOB-SH), that was tailored towards highly efficient simulation of charge transport in molecular materials, yet with nuclei treated classically. In this work we extend FOB-SH and include nuclear quantum effects by combining it with ring-polymer molecular dynamics (RPMD) in three different flavours (i) RPSH with bead approximation (RPSH-BA) as suggested in [Shushkov et al., J. Chem. Phys., 2012, 137, 22A549], (ii) a modification of (i) denoted RPSH with weighted bead approximation (RPSH-wBA) and (iii) the isormorphic Hamiltonian method of [Tao et al., J. Chem. Phys., 2018, 148, 10237] (SH-RP-iso). We present here applications to hole transfer in a molecular dimer model and analyze detailed balance and internal consistency of all three methods and investigate the temperature and driving force dependence of the hole transfer rate. We find that RPSH-BA strongly underestimates and RPSH-wBA overestimates the exact excited state population, while SH-RP-iso gives satisfactory results. We also find that the latter predicts a flattening of the rate vs driving force dependence in the Marcus’s inverted regime at low temperature, as often observed experimentally. Overall, our results suggest that FOB-SH combined with SH-RP-iso is a promising method for including zero point motion and tunneling in charge transport simulations in molecular materials and biological systems.

Type: Article
Title: Nonadiabatic dynamics with quantum nuclei: Simulating charge transfer with ring polymer surface hopping
DOI: 10.1039/c9fd00046a
Publisher version: https://doi.org/10.1039/c9fd00046a
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
UCL classification: UCL > Provost and Vice Provost Offices
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy
URI: http://discovery.ucl.ac.uk/id/eprint/10080655
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