Overcoming positivity violations for density matrices in surface hopping

Anna S. Bondarenko, Roel Tempelaar*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Scopus citations


Fewest-switches surface hopping (FSSH) has emerged as one of the leading methods for modeling the quantum dynamics of molecular systems. While its original formulation was limited to adiabatic populations, the growing interest in the application of FSSH to coherent phenomena prompts the question of how one should construct a complete density matrix based on FSSH trajectories. A straightforward solution is to define adiabatic coherences based on wavefunction coefficients. In this paper, we demonstrate that inconsistencies introduced in the density matrix through such treatment may lead to a violation of positivity. We furthermore show that a recently proposed coherent generalization of FSSH results in density matrices that satisfy positivity while yielding improved accuracy throughout much (but not all) of parameter space.

Original languageEnglish (US)
Article number054117
JournalJournal of Chemical Physics
Issue number5
StatePublished - Feb 7 2023

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry


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