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The Journal of Chemical Physics

Exchange energy in a double-well potential profile from fluctuation theory

Michele Battezzati, Valerio Magnasco

Published Feb 22, 2001• 9 citations
Publisher

Abstract

This article shows that the asymptotic quantum mechanical exchange energies and wave functions in a bistable potential can be obtained by computing the complex-valued first-passage time across the potential barrier from a transient state endowed with Smoluchowski boundary conditions, whose probability density is concentrated on one side of the barrier. This interpretation is validated by one of the authors’ previous work on diffusion in a random field, showing that this model yields a diffusion equation equivalent to quantum mechanical equations.

DOI
10.1063/1.1340580

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This article shows that the asymptotic quantum mechanical exchange energies and wave functions in a bistable potential can be obtained by computing the complex-valued first-passage time across the potential barrier from a transient state endowed with Smoluchowski boundary conditions, whose probability density is concentrated on one side of the barrier. This interpretation is validated by one of the authors’ previous work on diffusion in a random field, showing that this model yields a diffusion equation equivalent to quantum mechanical equations.
Nelson's stochastic mechanics formulates quantum dynamics as a real-time conservative diffusion process in which a particle undergoes Brownian-like motion with a fluctuation amplitude fixed by Planck's constant. While being mathematically equivalent to the Schrödinger formulation, this approach provides an alternative dynamical framework that enables the study of time-resolved quantities that are not straightforwardly defined within the standard operator-based approach. In the present work, Nelson's stochastic mechanics is employed to investigate tunneling-time statistics for bound states in double-well potentials. Using first-passage time theory within this framework, both the mean tunneling time, τˉ\barττˉ, and the full probability distribution, p(τ)p(τ)p(τ), are computed. The theoretical predictions are validated through extensive numerical simulations of stochastic trajectories for two representative potentials. For the square double-well potential, analytical expressions for τˉ\barττˉ are derived and are shown to be in excellent agreement with simulations. In the high-barrier limit, the results reveal a direct relation between the stochastic-mechanical and quantum-mechanical tunneling times, expressed as τQM=(π/2)τˉτ_{\mathrm{QM}} = (π/2)\barττQM​=(π/2)τˉ, where τQMτ_{\mathrm{QM}}τQM​ corresponds to half the oscillation period of the probability of finding the particle in either well. This relation is further confirmed for generic double-well systems through a WKB analysis. As a concrete application, the inversion dynamics of the ammonia molecule is analyzed, yielding an inversion frequency of approximately 24 GHz, in close agreement with experimental observations. These results highlight the potential of stochastic mechanics as a conceptually coherent and quantitatively consistent framework for analyzing tunneling phenomena in quantum systems.
Abstract Stochastic fluctuation of barrier height and width of a symmetric double well plays a very significant role in the corresponding dynamics by increasing the semiclassical transmission probability and Shannon entropy of the system. The population of the system has been observed to be spread into several under barrier states starting from the or [ , where and are the wave functions describing the two lowest degenerate states] in presence of the stochastic fluctuation. This distribution over several states is manifested by steady increase in Shannon entropy. However, any arbitrary value of the stochastic fluctuation cannot increase the populations of the upper energy states and consequently no gain in the net value of Shannon entropy results. There is an optimum frequency for which the Shannon entropy passes through a maximum, which is also found out in this work. We have also calculated the semiclassical WKB like transmission probability as a function of time and it is clear that the random fluctuation of barrier causes the transmission probability to increase to a significant amount. As the total energy of the system remains below the potential barrier, this transmission probability is equivalent to tunneling probability. It has been clearly shown that if the fluctuation is made to be periodic (without changing the frequency and magnitude of the fluctuation) it cannot effect any significant change in the overall dynamics.
The time evolution of quantum mechanical states in a square well of infinite depth with a Dirac δ function at its center has been examined for cases where the initial state was localized in one of the wells. Let well A denote the well in which the initial state is localized, and let P(t) denote the integrated probability density Ψ*Ψ in well A. For opaque barriers the time-dependent system is adequately described by a two-state model in which only the pair of stationary states of even and odd parity are considered whose wave functions in well A, apart from an arbitrary phase factor, are largely identical with the wave function of the initial state. For P(t) a harmonic oscillation is observed whose frequency νt is well approximated by the well-known formula for the tunneling frequency νt≂ΔE/h, where ΔE represents the energy separation among the pair of states in the model. For the present model of a symmetric double well it has been shown that for highly transparent barriers a three-state model can describe the time evolution adequately. The three stationary states involved in this model are a state of odd parity whose wave function in well A is largely the same as the wave function of the initial state and a pair of stationary states of even parity which on the energy scale are immediately above and below the first state. In this three-state model the function P(t) is a superposition of two sinusoidal functions with nearly identical amplitudes and frequencies plus a constant. As a consequence, the amplitude of P(t) changes harmonically. In the present model a δ function has been used as a barrier in order to minimize the mathematical detail involved in the time-dependent treatment. It is to be expected that the beating in P(t) can be observed also in the time evolution of a state localized in one of the wells of a symmetric double-minimum potential with a more realistic ‘‘low’’ barrier if the density of energy levels near the energies of the levels to be considered in the corresponding three-state model varies slowly with energy.
Abstract The transient properties of a Brownian particle moving in a bistable system with quantum corrections are investigated. The Quantum Smoluchowski Equation (QSE) is fully valid for high temperatures; for low temperatures it is valid only in a restricted domain of the state space. The quantum effects in a bistable system stand out for low temperatures. Explicit expressions of the mean first-passage time (MFPT) are obtained by using a steepest-descent approximation. The quantum effects are against the particle moving towards the destination from its original position.
An exact analytic solution of the time-dependent Schrödinger equation with cutoff wave initial conditions, that goes into the stationary solution at asymptotically long times, is used to investigate the transient behavior in the time evolution of the probability density along the internal and transmitted regions of a potential barrier. The approach involves the complex poles and residues (resonant states) of the outgoing Green's function of the problem. The solution exhibits absence of propagation along the classically forbidden internal region of the potential, and along the transmitted region it splits into two propagating structures. One of them is a transient effect describing the earliest response of the system to the initial condition whereas the other structure evolves towards the stationary solution.
The Schrödinger equation is reformulated as a universal continuity equation, which connects between changes in the particles probability density distribution to probability current densities (fluxes). The formulation of particle conservation in terms of stationary fluxes enables one to associate stationary wave functions also to open quantum systems characterized by stationary particle currents. These functions are (improper) solutions of the stationary Schrödinger equation, obtained under scattering boundary conditions. These boundary conditions can be fulfilled for any positive asymptotic kinetic energy, hence, the energy spectrum of the scattering states is continuous. We demonstrate flux calculations in scattering through a one-dimensional potential energy well/barrier, focusing on transmission and reflection probabilities. Nonclassical phenomena such as transmission at energies below a potential energy barrier (quantum tunneling), or reflections at energies above a potential energy well are analyzed. The phenomenon of full transmission through a double barrier structure (resonant tunneling) is introduced in the context of nanoscale transport.