The stochastic dynamics of a Brownian particle driven by a space-dependent, rapidly oscillating time-periodic potential (with frequency ω) has been addressed in the quantum regime within the framework of time-dependent system-reservoir Hamiltonian. Employing Floquet theorem in conjunction with the idea of separation of time scales, we construct a Langevin equation (containing a static effective potential) by exploiting a systematic perturbative expansion in powers of ω −1 . We compute the escape rate from the meta-stable state using the corresponding quantum Smoluchowski equation and observe a "resonance phenomenon" which is a signature of systemreservoir quantization. This work can be used to model the trapping mechanism as well as the quantum-fluctuation-induced escape process from the trap.

In this article we explore the dynamics of escape of a particle in the semiclassical regime by driving the particle externally. We demonstrate that under suitable approximations the semiclassical escape rate essentially assumes the structure of classical Kramers rate. Both internal (due to thermal bath) as well as external noises (due to driving) are being considered. The noises are stationary, Gaussian, and are characterized by arbitrary decaying memory kernel. Finally, we subject our formulation to rigorous numerical test under variedly changing conditions of the parameters.

No abstract

The present investigation reports on the prospect of using state specific multireference perturbation theory (SSMRPT) with an improved virtual orbital complete active space configuration interaction (IVO-CASCI) reference function (IVO-SSMRPT) to generate potential energy surfaces (PESs) for molecular systems [such as CH, CH, CH, HO, LiH, and KN] by stretching and breaking of suitable bonds with modest basis sets. We have also revisited the dissociation energy profile of triplet ketene which exhibits a step-like structure in the observed rate. The application of the method has also been made to the ionization energies of HO. Although the perturbative corrections are obtained by the diagonalization of the effective Hamiltonian, in IVO-SSMRPT, only one physically relevant solution is achievable. It is parameter free and does not require any threshold to avoid the intruder problem. It is strictly size-extensive and size-consistent provided that local orbitals are used. The PESs obtained with our approach are smooth all along the reaction path. Our estimates are in close agreement with the available reference data indicating that IVO-SSMRPT is a robust paradigm for the accurate computation of ground, excited and ionized states as it captures the mutual inter-play of different flavors of correlation effects in a balanced and accurate way.

We explore the Brownian dynamics in the quantum regime (by investigating the quantum Langevin and Smoluchowski equations) in terms of an effective time-independent Hamiltonian in the presence of a rapidly oscillating field. We achieve this by systematically expanding the time-dependent system-reservoir Hamiltonian in the inverse of driving frequency with a systematic time-scale separation and invoking a quantum gauge transformation within the framework of Floquet theorem.