Quantum information scrambling and chemical reactions

Chenghao Zhang, Sohang Kundu, Nancy Makri, Martin Gruebele, Peter G. Wolynes

Research output: Contribution to journalArticlepeer-review

Abstract

The ultimate regularity of quantum mechanics creates a tension with the assumption of classical chaos used in many of our pictures of chemical reaction dynamics. Out-of-time-order correlators (OTOCs) provide a quantum analog to the Lyapunov exponents that characterize classical chaotic motion. Maldacena, Shenker, and Stanford have suggested a fundamental quantum bound for the rate of information scrambling, which resembles a limit suggested by Herzfeld for chemical reaction rates. Here, we use OTOCs to study model reactions based on a double-well reaction coordinate coupled to anharmonic oscillators or to a continuum oscillator bath. Upon cooling, as one enters the tunneling regime where the reaction rate does not strongly depend on temperature, the quantum Lyapunov exponent can approach the scrambling bound and the effective reaction rate obtained from a population correlation function can approach the Herzfeld limit on reaction rates: Tunneling increases scrambling by expanding the state space available to the system. The coupling of a dissipative continuum bath to the reaction coordinate reduces the scrambling rate obtained from the early-time OTOC, thus making the scrambling bound harder to reach, in the same way that friction is known to lower the temperature at which thermally activated barrier crossing goes over to the low-temperature activationless tunneling regime. Thus, chemical reactions entering the tunneling regime can be information scramblers as powerful as the black holes to which the quantum Lyapunov exponent bound has usually been applied.

Original languageEnglish (US)
Article numbere2321668121
Pages (from-to)e2321668121
JournalProceedings of the National Academy of Sciences of the United States of America
Volume121
Issue number15
DOIs
StatePublished - Apr 9 2024

Keywords

  • activation energy
  • black holes
  • path integral
  • quantum chaos
  • wavefunction

ASJC Scopus subject areas

  • General

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