Numerical simulation of transmission coefficient using c-number Langevin equation

We numerically implement the reactive flux formalism on the basis of a recently proposed c-number Langevin equation [Barik \textit{et al}, J. Chem. Phys. {\bf 119}, 680 (2003); Banerjee \textit{et al}, Phys. Rev. E {\bf 65}, 021109 (2002)] to calculate transmission coefficient. The Kramers' turnover, the $T^2$ enhancement of the rate at low temperatures and other related features of temporal behaviour of the transmission coefficient over a range of temperature down to absolute zero, noise correlation and friction are examined for a double well potential and compared with other known results. This simple method is based on canonical quantization and Wigner quasiclassical phase space function and takes care of quantum effects due to the system order by order

Noise correlation-induced splitting of Kramers' escape rate from a metastable state

A correlation between two noise processes driving the thermally activated particles in a symmetric triple well potential, may cause a symmetry breaking and a difference in relative stability of the two side wells with respect to the middle one. This leads to an asymmetric localization of population and splitting of Kramers' rate of escape from the middle well, ensuring a preferential distribution of the products in the course of a parallel reaction

Quantum Kramers' equation for energy diffusion and barrier crossing dynamics in the low friction regime

Based on a true phase space probability distribution function and an ensemble averaging procedure we have recently developed [Phys. Rev. E 65, 021109 (2002)] a non-Markovian quantum Kramers' equation to derive the quantum rate coefficient for barrier crossing due to thermal activation and tunneling in the intermediate to strong friction regime. We complement and extend this approach to weak friction regime to derive quantum Kramers' equation in energy space and the rate of decay from a metastable well. The theory is valid for arbitrary temperature and noise correlation. We show that depending on the nature of the potential there may be a net reduction of the total quantum rate below its corresponding classical value which is in conformity with earlier observation. The method is independent of path integral approaches and takes care of quantum effects to all orders.Comment: 26 pages, RevTe

Chaos and information entropy production

We consider a general N-degrees-of-freedom nonlinear system which is chaotic and dissipative, and show that the nature of chaotic diffusion is reflected in the correlation of fluctuation of the linear stability matrix for the equation of motion of the dynamical system whose phase space variables behave as stochastic variables in the chaotic regime. Based on a Fokker-Planck description of the system in the associated tangent space and an information entropy balance equation, a relationship between chaotic diffusion and the thermodynamically inspired quantities such as entropy production and entropy flux is established. The theoretical propositions have been verified by numerical experiments

Quantum escape kinetics over a fluctuating barrier

The escape rate of a particle over a fluctuating barrier in a double well potential exhibits resonance at an optimum value of correlation time of fluctuation. This has been shown to be important in several variants of kinetic model of chemical reactions . We extend the analysis of this phenomenon of resonant activation to quantum domain to show how quantization significantly enhances resonant activation at low temperature due to tunneling

Interference of stochastic resonances: Splitting of Kramers' rate

We consider the escape of particles located in the middle well of a symmetric triple well potential driven sinusoidally by two forces such that the potential wells roll as in stochastic resonance and the height of the potential barrier oscillates symmetrically about a mean as in resonant activation. It has been shown that depending on their phase difference the application of these two synchronized signals may lead to a splitting of time averaged Kramers' escape rate and a preferential product distribution in a parallel chemical reaction in the steady state