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Self-Consistent Filtering Scheme for Efficient Calculations of Observables via the Mixed Quantum-Classical Liouville Approach.

Research paper by David D Dell'Angelo, Gabriel G Hanna

Indexed on: 06 Jan '16Published on: 06 Jan '16Published in: Journal of Chemical Theory and Computation



Abstract

Over the past decade, several algorithms have been developed for calculating observables using mixed quantum-classical Liouville dynamics, which differ in how accurately they solve the quantum-classical Liouville equation (QCLE). One of these algorithms, known as sequential short-time propagation (SSTP), is a surface-hopping algorithm that solves the QCLE almost exactly, but obtaining converged values of observables requires very large ensembles of trajectories due to the rapidly growing statistical errors inherent to this algorithm. To reduce the ensemble sizes, two filtering schemes (viz., observable cutting and transition filtering) have been previously developed and effectively applied to both simple and complex models. However, these schemes are either ad hoc in nature or require significant trial and error for them to work as intended. In this study, we present a self-consistent scheme, which, in combination with a soundly motivated probability function used for the Monte Carlo sampling of the nonadiabatic transitions, avoids the ad hoc observable cutting and reduces the amount of trial and error required for the transition filtering to work. This scheme is tested on the spin-boson model, in the weak, intermediate, and strong coupling regimes. Our transition filtered results obtained using a newly proposed probability function, which favors the sampling of nonadiabatic transitions with small energy gaps, show a significant improvement in accuracy and efficiency for all coupling regimes over the results obtained using observable cutting and the original implementation of transition filtering and are comparable to those obtained using the combination of these two techniques. It is therefore expected that this novel scheme will substantially reduce ensemble sizes and simplify the computation of observables in more complex systems.