Pradipta Ghosh

Revisiting the ‘cis-effect’ in 1,2-difluoro derivatives of ethylene and diazene using ab initio multireference methods

The relative stabilities of cis- and trans- isomers of 1,2-difluoroethylene and 1,2-difluorodiazene have been studied via the state-specific multireference coupled cluster (SS-MRCC) method and its perturbative counterpart through the computation of the optimised structures and corresponding energies. Despite the existence of several cis-destabilising mechanisms, present calculations reveal the energetic preference of the cis- isomer (the cis-effect) for the systems considered here. Differences in structural parameters and vibrational frequencies among cis- and trans- isomers have been discussed. Very good agreement of our estimates has been found with the benchmark theoretical and experimental results. The SS-MRCC methods produce a smooth and consistent behaviour across the entire torsional surface for the cis–trans isomerisation indicating that the method has sufficient flexibility to model large changes in electronic structure that accompany chemical changes.

Improved virtual orbitals in state specific multireference perturbation theory for prototypes of quasidegenerate electronic structure

The state-specific multireference perturbation theory (SSMRPT) with an improved virtual orbital complete active space configuration interaction (IVO-CASCI) reference function [called as IVO-SSMRPT] is used to investigate the energy surface, geometrical parameters, molecular properties of spectroscopic interest for the systems/situations [such as BeH2, BeCH2, MgCH2, Si2H4, unimolecular dissociation of H2CO, and intramolecular reaction pathways of 1,3-butadiene] where the effect of quasidegeneracy cannot be neglected. The merit of using the IVO-CASCI rather than complete active space self-consistent field (CASSCF) is that it is free from iterations beyond those in the initial SCF calculation and the convergence difficulties that plague CASSCF calculations with increasing size of the CAS. While IVO-CASCI describes the non-dynamical correlation, the SSMRPT scheme is a good second-order perturbative approximation to account for the rest of the correlation energy. Our IVO-SSMRPT method is instrumental in avoiding intruder states in an size-extensive manner and allows the revision of the content of wave function in the model space. It can treat model as well as real systems with predictive accuracy, as is evident from the fairly nice accordance between our estimates, and high-level theoretical results. Our estimates also corroborate well with some experimental findings.

A semiclassical approach to explore the bistable kinetics of a Brownian particle in a nonequilibrium environment

We explore the noise-induced barrier crossing dynamics of a Brownian particle in the high temperature quantum regime under large damping. We assume the associated heat bath not to be in thermal equilibrium; it is rather driven by an externally applied random force which exposes the system particles to a nonequilibrium environment. We propose a system + reservoir model to study the stochastic Langevin dynamics. We also construct the corresponding Fokker–Planck equation in the said regime and solve it to explore the bistable kinetics. We investigate the role of different parameters in shaping the nature of such a bistable kinetics in detail and hence allowing one to get some insight into the very complicated dynamics of quantum dissipative system(s). Finally, we analyze the semiclassical rate vis-a-vis the classical analog.

A microscopic model for noise induced transport: Heat-bath nonlinearly driven by external white noise

This work explores the observation that, even in the absence of a net externally applied bias, a symmetric homogeneous system coupled linearly to two heat baths is capable of producing unidirectional motion simply by nonlinearly driving one of the heat baths by an external Gaussian white noise. This is quite contrary to the traditional observation that, in order to obtain a net drift current, a state-dependent dissipation, which is a consequence of nonlinear system-bath coupling, is ubiquitous.

Stochastic resonance in a generalized quantum Kubo oscillator.

We discuss stochastic resonance in a biased linear quantum system that is subject to multiplicative and additive noises. Starting from a microscopic system-reservoir Hamiltonian, we derive a c-number analogue of the generalized Langevin equation. The developed approach puts forth a quantum mechanical generalization of the Kubo type oscillator which is a linear system. Such a system is often used in the literature to study various phenomena in nonequilibrium systems via a particular interaction between system and the external noise. Our analytical results proposed here have the ability to reveal the role of external noise and vis-a-vis the mechanisms and detection of subtle underlying signatures of the stochastic resonance behavior in a linear system. In our development, we show that only when the external noise possesses a finite correlation time the quantum effect begins to appear. We observe that the quantum effect enhances the resonance in comparison to the classical one.

Escape of a driven particle from a metastable state: A semiclassical approach

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.

On the conversion XCN ⟷ XNC via an efficient and economic perturbative wave function approach

ABSTRACT The energetics, structures, reaction paths and mechanisms for the conversion XCN ⟷ XNC, with X = H, Li, CH3 and H2B have been investigated through the use of improved virtual orbitals (IVO) in a second-order multireference perturbation theory (MRPT) treatment within the framework of state-specific (SS) parametrisation of the wave function for the target state (IVO-SSMRPT). Due to its flexibility, IVO-SSMRPT formulation allows us to take into account the major part of the coupling between the dynamic and nondynamic correlation effects in an accurate manner. The results obtained by our calculations agree well with the state-of-the-art electronic structure methods and reference values which illustrates that IVO-SSMRPT, when applied judiciously, can be very accurate for reaction surfaces of XCN ⟷ XNC isomerisation, barrier and bond-parameters.