On the basis of a coherent state representation of quantum noise operator and an ensemble averaging procedure a scheme for quantum Brownian motion has been proposed recently [Banerjee {\it et al}, Phys. Rev. E {\bf65}, 021109 (2002); {\bf66}, 051105 (2002)]. We extend this approach to formulate reactive flux theory in terms of quantum phase space distribution functions and to derive a time dependent quantum transmission coefficient - a quantum analogue of classical Kramers'-Grote-Hynes coefficient in the spirit of Kohen and Tannor's classical formulation. The theory is valid for arbitrary noise correlation and temperature. The specific forms of this coefficient in the Markovian as well as in the non-Markovian limits have been worked out in detail for intermediate to strong damping regime with an analysis of quantum effects. While the classical transmission coefficient is independent of temperature, its quantum counterpart has significant temperature dependence particularly in the low temperature regime.
On the basis of a coherent state representation of quantum noise operator and an ensemble averaging procedure a scheme for quantum Brownian motion has been proposed recently [Banerjee {\it et al}, Phys. Rev. E {\bf65}, 021109 (2002); {\bf66}, 051105 (2002)]. We extend this approach to formulate reactive flux theory in terms of quantum phase space distribution functions and to derive a time dependent quantum transmission coefficient - a quantum analogue of classical Kramers'-Grote-Hynes coefficient in the spirit of Kohen and Tannor's classical formulation. The theory is valid for arbitrary noise correlation and temperature. The specific forms of this coefficient in the Markovian as well as in the non-Markovian limits have been worked out in detail for intermediate to strong damping regime with an analysis of quantum effects. While the classical transmission coefficient is independent of temperature, its quantum counterpart has significant temperature dependence particularly in the low temperature regime.
This work is about a quantum-mechanical generalisation of transition rate theory that accounts for temperature-dependent quantum-dynamical effects. The starting point of this investigation is a formulation of the classical transmission coefficient where the activated dynamics is needed to obtain the time evolution of the classical state function and the rate is expressed as an average flux in momentum space. Traditional approaches to quantum transition rate theory are briefly discussed, with emphasis on the fact that these do not generally require knowledge of the open quantum dynamics. The latter can be studied by means of the Lindblad equation for mixed states, which is shown to be analogous to an average over realisations of a certain type of stochastic Schrödinger dynamics. The stochastic evolution in Hilbert space is used in combination with an ansatz for the wave function as a Gaussian wave packet to show that under appropriate assumptions the stochastic Schrödinger equation converges to the classical Langevin equation. A novel formulation of the quantum transmission coefficient is presented which features a quantum-mechanical version of the state function obtained via the density operator, so that the activated quantum dynamics can be taken into account by solving the Lindblad equation. A numerical investigation of the quantum transmission coefficient thus obtained for different temperatures is carried out, along with a comparison to the classical results. The quantum-mechanical transmission coefficient is found to display some expected features, such as vanishing in the limit as t → 0, displaying a “plateau” value for certain values of the temperature, and decaying to zero exponentially fast when the fundamental assumptions of TRT do not hold. Additionally the plateau value of the quantum transmission coefficient is found to be smaller than the classical counterpart in all regimes, and to approach the corresponding classical value in the limit of large temperatures.
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.
Recent progress in our understanding of quantum effects on the Brownian motion in an external potential is reviewed. This problem is ubiquitous in physics and chemistry, particularly in the context of decay of metastable states, for example, the reversal of the magnetization of a single domain ferromagnetic particle, kinetics of a superconducting tunnelling junction, etc. Emphasis is laid on the establishment of master equations describing the diffusion process in phase space analogous to the classical Fokker-Planck equation. In particular, it is shown how Wigner's [E. P. Wigner, Phys. Rev., 1932, 40, 749] method of obtaining quantum corrections to the classical equilibrium Maxwell-Boltzmann distribution may be extended to the dissipative non-equilibrium dynamics governing the quantum Brownian motion in an external potential V(x), yielding a master equation for the Wigner distribution function W(x,p,t) in phase space (x,p). The explicit form of the master equation so obtained contains quantum correction terms up to o(h(4)) and in the classical limit, h --> 0, reduces to the classical Klein-Kramers equation. For a quantum oscillator, the method yields an evolution equation coinciding in all respects with that of Agarwal [G. S. Agarwal, Phys. Rev. A, 1971, 4, 739]. In the high dissipation limit, the master equation reduces to a semi-classical Smoluchowski equation describing non-inertial quantum diffusion in configuration space. The Wigner function formulation of quantum Brownian motion is further illustrated by finding quantum corrections to the Kramers escape rate, which, in appropriate limits, reduce to those yielded via quantum generalizations of reaction rate theory.
In this thesis, the recent semiclassical approach to quantum Brownian motion of Coffey et\nal. [Phys. Chem. Chem. Phys. 9, 3361 (2007)] is studied in detail. This approach is based\non a semiclassical extension of Wigner's method of obtaining corrections to the classical\nequilibrium Maxwell-Boltzmann distribution, yielding a master equation for the reduced\nWigner function in quasi-phase space valid in the weak coupling and high temperature\nlimits. In the non-inertial or high damping limit, this master equation reduces to a quantum\nSmoluchowksi equation (QSE), where the drift coefficient remains as in the classical case,\nwhile the diffusion coefficient is altered to include the quantum parameter and derivatives\nof the potential.
Based on a coherent state representation of noise operator and an ensemble averaging procedure we have recently developed [Phys. Rev. E {\bf 65}, 021109 (2002); {\it ibid.} 051106 (2002)] a scheme for quantum Brownian motion to derive the equations for time evolution of {\it true} probability distribution functions in c-number phase space. We extend the treatment to develop a numerical method for generation of c-number noise with arbitrary correlation and strength at any temperature, along with the solution of the associated generalized quantum Langevin equation. The method is illustrated with the help of a calculation of quantum mean first passage time in a cubic potential to demonstrate quantum Kramers turnover and quantum Arrhenius plot.
A coherent state phase space representation of operators, based on the Husimi distribution, is used to derive an exact expression for the symmetrized version of thermal correlation functions. In addition to the time and temperature independent phase space representation of the two operators whose correlation function is of interest, the integrand includes a non-negative distribution function where only one imaginary time and one real time propagation are needed to compute it. The methodology is exemplified for the flux side correlation function used in rate theory. The coherent state representation necessitates the use of a smeared Gaussian flux operator whose coherent state phase space representation is identical to the classical flux expression. The resulting coherent state expression for the flux side correlation function has a number of advantages as compared to previous formulations. Since only one time propagation is needed, it is much easier to converge it with a semiclassical initial value representation. There is no need for forward-backward approximations, and in principle, the computation may be implemented on the fly. It also provides a route for analytic semiclassical approximations for the thermal rate, as exemplified by a computation of the transmission factor through symmetric and asymmetric Eckart barriers using a thawed Gaussian approximation for both imaginary and real time propagations. As a by-product, this example shows that one may obtain "good" tunneling rates using only above barrier classical trajectories even in the deep tunneling regime.