Quantum rate constants from short-time dynamics: An analytic continuation approach

Eun Ji Sim, Goran Krilov, B. J. Berne

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

A method for calculating the quantum canonical rate constant of chemical reactions in a many body system by means of a short-time flux autocorrelation function combined with a maximum entropy numerical analytic continuation scheme is presented. The rate constant is expressed as the time integral of the real-time flux autocorrelation function. The real-time flux autocorrelation function is evaluated for short times fully quantum mechanically by path integral Monte Carlo simulations. The maximum entropy approach is then used to extract the rate from the short real-time flux autocorrelation data. We present two numerical tests, one for proton transfer in harmonic dissipative environments in the deep tunneling regime and the other for the two-level model of primary charge separation in the photosynthetic reaction center. The results obtained using the flux autocorrelation data up to the time of no more than βℏ are in excellent agreement with the exact quantum calculation over a wide range of parameters including even the tunneling regime.

Original languageEnglish
Pages (from-to)2824-2833
Number of pages10
JournalJournal of Physical Chemistry A
Volume105
Issue number12
Publication statusPublished - 2001 Mar 29

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Autocorrelation
Rate constants
Fluxes
autocorrelation
Entropy
Photosynthetic Reaction Center Complex Proteins
Proton transfer
entropy
Chemical reactions
polarization (charge separation)
chemical reactions
harmonics
protons
simulation

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

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abstract = "A method for calculating the quantum canonical rate constant of chemical reactions in a many body system by means of a short-time flux autocorrelation function combined with a maximum entropy numerical analytic continuation scheme is presented. The rate constant is expressed as the time integral of the real-time flux autocorrelation function. The real-time flux autocorrelation function is evaluated for short times fully quantum mechanically by path integral Monte Carlo simulations. The maximum entropy approach is then used to extract the rate from the short real-time flux autocorrelation data. We present two numerical tests, one for proton transfer in harmonic dissipative environments in the deep tunneling regime and the other for the two-level model of primary charge separation in the photosynthetic reaction center. The results obtained using the flux autocorrelation data up to the time of no more than βℏ are in excellent agreement with the exact quantum calculation over a wide range of parameters including even the tunneling regime.",
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Quantum rate constants from short-time dynamics : An analytic continuation approach. / Sim, Eun Ji; Krilov, Goran; Berne, B. J.

In: Journal of Physical Chemistry A, Vol. 105, No. 12, 29.03.2001, p. 2824-2833.

Research output: Contribution to journalArticle

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