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Capturing electronic decoherence in quantum-classical dynamics using the ring-polymer-surface-hopping–density-matrix approach

Yashoj Shakya1,2,*, Ralph Welsch1,3, Ludger Inhester1,3,†, and Robin Santra1,2,3,‡

  • 1Center for Free-Electron Laser Science, Deutsches Elektronen-Synchrotron, Notkestraße 85, 22607 Hamburg, Germany
  • 2Department of Physics, Universität Hamburg, Notkestraße 9-11, 22607 Hamburg, Germany
  • 3Hamburg Centre for Ultrafast Imaging, Luruper Chaussee 149, 22761 Hamburg, Germany

  • *yashoj.shakya@desy.de
  • †ludger.inhester@cfel.de
  • ‡robin.santra@cfel.de
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Phys. Rev. A 107, 062810 – Published 12 June, 2023

DOI: https://doi.org/10.1103/PhysRevA.107.062810

Abstract

Simulations of coupled electronic and nuclear dynamics in molecules can be quite challenging due to the involved interplay of the many degrees of freedom. Because a full quantum treatment of both electrons and nuclei is computationally very demanding, it is generally restricted to model systems or rather small molecules and short timescales. Mixed quantum-classical dynamics methods such as Tully's fewest switches surface hopping (FSSH) can be used to overcome this limitation. However, FSSH is known to poorly describe electronic coherences and decoherence phenomena. Here, we present an approach that combines FSSH with ring-polymer molecular dynamics (RPMD) in a specific way that aims to alleviate the coherence problem. Termed the ring-polymer-surface-hopping–density-matrix approach, this method uses an electronic density-matrix formulation to calculate surface hopping rates. This incorporates decoherence effects into FSSH in a natural way by taking into account the spatial spreading of the ring polymer that mimics the width of a nuclear wave packet in each RPMD trajectory. By applying our method to Tully's one-dimensional model system, we demonstrate that this method captures a crucial decoherence mechanism that is missing in FSSH. Furthermore, our method turns out to be superior at describing electronic coherences compared with earlier attempts at combining RPMD and FSSH.

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Phys. Rev. A 107, 062810– Published 12 June, 2023
  • Received 15 February 2023
  • Accepted 3 April 2023
Article part of CHORUS
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