Quantum State-to-State Rates for Multistate Processes from Coherences

Reshmi Dani, Nancy Makri

Research output: Contribution to journalArticlepeer-review

Abstract

For a multistate system coupled to a general environment through terms local in the system basis, we show that the time derivatives of populations are given in terms of imaginary components of coherences, i.e., off-diagonal elements of the reduced density matrix. When the process exhibits rate dynamics, we show that all state-to-state rates can be obtained from the early "plateau"values of these imaginary components. The evolution of the state populations is then obtained from the short-time simulation results and the solution of the kinetic equations with the computed rate matrix. These expressions generalize the reactive flux method and its nonequilibrium version to multistate processes and show that even in the completely incoherent limit of rate kinetics, the time evolution of populations is governed by coherences. Further, we show that by virtue of detailed balance, the short-time values of the imaginary components of coherences fully determine the equilibrium populations.

Original languageEnglish (US)
Pages (from-to)8141-8149
Number of pages9
JournalJournal of Physical Chemistry Letters
DOIs
StatePublished - Sep 1 2022

ASJC Scopus subject areas

  • General Materials Science
  • Physical and Theoretical Chemistry

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