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The Journal of Physical Chemistry B

Thermal and Quantum Barrier Passage as Potential-Driven Markovian Dynamics

Aleksei M. Zheltikov

Published Oct 31, 2023• 4 citations
Publisher

Abstract

Rapidly progressing laser technologies provide powerful tools to study potential barrier-passage dynamics in physical, chemical, and biological systems with unprecedented temporal and spatial resolution and a remarkable chemical and structural specificity. The available theories of barrier passage, however, operate with equations, potentials, and parameters that are best suited for a specific area of research and a specific class of systems and processes. Making connections among these theories is often anything but easy. Here, we address this problem by presenting a unified framework for the description of a vast variety of classical and quantum barrier-passage phenomena, revealing an innate connection between various types of barrier-passage dynamics and providing closed-form equations showing how the signature exponentials in classical and quantum barrier-passage rates relate to and translate into each other. In this framework, the Arrhenius-law kinetics, the emergence of the Gibbs distribution, Hund's molecular wave-packet well-to-well oscillatory dynamics, Keldysh photoionization, and Kramers' escape over a potential barrier are all understood as manifestations of a potential-driven Markovian dynamics whereby a system evolves from a state of local stability. Key to the irreducibility of quantum tunneling to thermally activated barrier passage is the difference in the ways the diffusion-driving potentials emerge in these two tunneling settings, giving rise to stationary states with a distinctly different structure.

DOI
10.1021/acs.jpcb.3c02744

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Rapidly progressing laser technologies provide powerful tools to study potential barrier-passage dynamics in physical, chemical, and biological systems with unprecedented temporal and spatial resolution and a remarkable chemical and structural specificity. The available theories of barrier passage, however, operate with equations, potentials, and parameters that are best suited for a specific area of research and a specific class of systems and processes. Making connections among these theories is often anything but easy. Here, we address this problem by presenting a unified framework for the description of a vast variety of classical and quantum barrier-passage phenomena, revealing an innate connection between various types of barrier-passage dynamics and providing closed-form equations showing how the signature exponentials in classical and quantum barrier-passage rates relate to and translate into each other. In this framework, the Arrhenius-law kinetics, the emergence of the Gibbs distribution, Hund's molecular wave-packet well-to-well oscillatory dynamics, Keldysh photoionization, and Kramers' escape over a potential barrier are all understood as manifestations of a potential-driven Markovian dynamics whereby a system evolves from a state of local stability. Key to the irreducibility of quantum tunneling to thermally activated barrier passage is the difference in the ways the diffusion-driving potentials emerge in these two tunneling settings, giving rise to stationary states with a distinctly different structure.
The notion of the first passage time is shown to offer a meaningful extension to quantum tunneling, providing a closed-integral-form analytical unification of the tunneling rate and the tunneling passage time. We demonstrate that, in suitable potential settings, the quantum first passage time, found as a solution to the Fokker-Planck and backward Kolmogorov's equations for the quantum probability density, recovers the hallmark results for the Kramers escape rate, the lifetime of tunneling quasi-stationary wave packets, leads to a classical, distance-over-speed passage time for a free-particle wave function, and offers useful insights into Keldysh's intimation on the electron barrier-traversal time in field-induced ionization.
We have presented a simple approach to quantum theory of Brownian motion and barrier crossing dynamics. Based on an initial coherent state representation of bath oscillators and an equilibrium canonical distribution of quantum-mechanical mean values of their co-ordinates and momenta we have derived a c number generalized quantum Langevin equation. The approach allows us to implement the method of classical non-Markovian Brownian motion to realize an exact generalized non-Markovian quantum Kramers' equation. The equation is valid for arbitrary temperature and friction. We have solved this equation in the spatial diffusion-limited regime to derive quantum Kramers' rate of barrier crossing and analyze its variation as a function of the temperature and friction. While almost all the earlier theories rest on quasiprobability distribution functions (e.g., Wigner function) and path integral methods, the present work is based on true probability distribution functions and is independent of path integral techniques. The theory is a natural extension of the classical theory to quantum domain and provides a unified description of thermally activated processes and tunneling.
Department of Chemistry, Visva-Bharati, Shantiniketan-731 235, India indian Association for the Cultivation of Science, Jadavpur, Kolkata-700 032, India E-mail : pcdsr@mahendra.iacs.res.in Fax: 91-33-24722805 Max-Pianck-Institut fur Physik Komplexer Systeme, Nothnitzer Strabe 38, 01187 Dresden, Germany Manuscript received 12 November 2002 Arrhenius rate law is now more than hundred years old. The dynamical basis of this phenomenological law was provided by Kramers in early nineteenforties. Since late seventies, the extensive experimental investigation in chemical dynamics and allied areas centered around Kramers' dynamical rate theory. The present paper is an outline of further development of rate theory in quantum mechanical context which takes into account of thermal activation and tunneling within an unified description. The theory is based on a new scheme for quantum Brownian motion recently proposed by us to establish quantum analogues of Kramers', Smoluchowski and Fokker-Pianck equations with true probability distribution functions in c-number phase space.
The quantum-mechanical version of the Kramers turnover problem is considered. The multidimensional character of the problem is taken into account via transformation to normal modes. This eliminates the coupling to the bath near the barrier top allowing the use of a simple harmonic transmission coefficient for the barrier dynamics. The well dynamics is described by a continuum form of a master equation for the energy in the unstable normal mode. Within first-order perturbation theory, the equations of motion for the stable normal modes have the form of a forced oscillator. The transition probability kernel is found using the known solution for the quantum forced oscillator problem. An expression for the quantum escape rate is derived. It encompasses all previously known limiting results in the thermally activated tunneling regime. The depopulation factor, which accounts for the nonequilibrium energy distribution is evaluated. The quantum transition probability kernel is broader than the classical and is skewed towards lower energies. Interplay between these two effects, together with a positive tunneling contribution, determines the relative magnitude of the quantum rate compared to the classical one. The theory is valid for arbitrary dissipation. Its use is illustrated for the case of a cubic potential with Ohmic (Markovian) dissipation.
Quantum tunneling is conventionally described by the Schrödinger wave equation with a prescribed static potential barrier, providing accurate transmission probabilities but offering limited insight into the microscopic dynamics of particle–barrier interactions. In this work, we develop a dynamical second-quantization framework in which the barrier is modeled as an ensemble of quantized internal modes rather than as an externally imposed classical potential. The tunneling particle interacts directly with these microscopic barrier excitations through a coupled particle–barrier Hamiltonian, from which the Heisenberg equations of motion are derived. Collective coherent excitations of the barrier modes give rise to an emergent effective barrier that naturally recovers the conventional rectangular barrier and the WKB transmission limit under appropriate conditions. Unlike standard treatments, the present formulation explicitly incorporates microscopic barrier dynamics and provides a unified description of particle–barrier coupling within a second-quantized formalism. The framework further suggests that repeated tunneling events may experience different microscopic interaction histories, motivating a statistical interpretation of tunneling times. Because both the particle and barrier are treated within the same operator formalism, the theory provides a natural foundation for extension to relativistic quantum transport, photonic barriers, cavity quantum electrodynamics, and other structured quantum media.
Since the early days of quantum mechanics, tunneling has been recognized as one of the hallmarks of the wave character of microscopic physics. The possibility of a quantum particle to penetrate an energetic barrier represents certainly one of the most spectacular implications of quantum theory and has led to various applications in nuclear, atomic, and molecular physics as well as in mesoscopic science. Typical scenarios in which tunneling manifests are the escape route of a quantum particle from a quasibounded region, the transition between two or more symmetry-related, but classically disconnected wells (which we shall focus on in the following), as well as scattering or transport through potential barriers. The spectrum of scenarios becomes even richer when the concept of tunneling is generalized to any kind of classically forbidden transitions in phase space, that is, to transitions that are not necessarily inhibited by static potential barriers but by some other constraints of the underlying classical dynamics (such as integrals of motion). Such “dynamical tunneling” processes arise frequently in molecular systems [1] and were realized with cold atoms propagating in periodically modulated optical lattices [2-4]. Moreover, the electromagnetic analog of dynamical tunneling was also obtained with microwaves in billiards [5].