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.
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Quantum scrambling of observable algebras
In this paper we describe an algebraic/geometrical approach to quantum scrambling. Generalized quantum subsystems are described by an hermitian-closed unital subalgebra A of operators evolving through a unitary channel. Qualitatively, quantum scrambling is defined by how the associated physical degrees of freedom get mixed up with others by the dynamics. Quantitatively, this is accomplished by introducing a measure, the geometric algebra anti-correlator (GAAC), of the self-orthogonalization of the commutant of A induced by the dynamics. This approach extends and unifies averaged bipartite OTOC, operator entanglement, coherence generating power and Loschmidt echo. Each of these concepts is indeed recovered by a special choice of A . We compute typical values of GAAC for random unitaries, we prove upper bounds and characterize their saturation. For generic energy spectrum we find explicit expressions for the infinite-time average of the GAAC which encode the relation between A and the full system of Hamiltonian eigenstates. Finally, a notion of A -chaoticity is suggested.
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- Award ID(s):
- 1819189
- PAR ID:
- 10339619
- Date Published:
- Journal Name:
- Quantum
- Volume:
- 6
- ISSN:
- 2521-327X
- Page Range / eLocation ID:
- 666
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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