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Fewest-switches surface hopping is studied in the context of quantum-classical Liouville dynamics. Both approaches are mixed quantum-classical theories that provide a way to describe and simulate the nonadiabatic quantum dynamics of…

Quantum Physics · Physics 2016-05-27 Raymond Kapral

We present a nonadiabatic classical-trajectory approach that offers the best of both worlds between fewest-switches surface hopping (FSSH) and quasiclassical mapping dynamics. This mapping approach to surface hopping (MASH) propagates the…

Chemical Physics · Physics 2023-03-29 Jonathan R. Mannouch , Jeremy O. Richardson

The quantum-classical Liouville equation describes the dynamics of a quantum subsystem coupled to a classical environment. It has been simulated using various methods, notably, surface-hopping schemes. A representation of this equation in…

Other Condensed Matter · Physics 2010-11-17 Hyojoon Kim , Ali Nassimi , Raymond Kapral

Accurate simulation the many-electronic nonadiabatic dynamics process at metal surfaces remains as a significant task. In this work, we present an orbital surface hopping (OSH) algorithm rigorously derived from the orbital quantum classical…

Chemical Physics · Physics 2025-11-24 Yong-Tao Ma , Rui-Hao Bi , Wenjie Dou

Mixed-quantum-classical molecular dynamics simulation implies an effective measurement on the electronic states owing to continuously tracking the atomic forces.Based on this insight, we propose a quantum trajectory mean-field approach for…

Chemical Physics · Physics 2014-08-08 Wei Feng , Luting Xu , Xin-Qi Li , Weihai Fang , YiJing Yan

We study a number of filtering schemes for the reduction of the statistical error in non-adiabatic calculations by means of the quantum-classical Liouville equation. In particular, we focus on a scheme based on setting a threshold value on…

Quantum Physics · Physics 2016-10-21 Daniel Uken , Alessandro Sergi , Francesco Petruccione

Surface hopping algorithms, as an important class of quantum dynamics simulation algorithms for non-adiabatic dynamics, are typically performed in the adiabatic representation, which can break down in the presence of ill-defined adiabatic…

Numerical Analysis · Mathematics 2022-05-06 Zhenning Cai , Di Fang , Jianfeng Lu

We revisit a recent proposal to model nonadiabatic problems with a complex-valued Hamiltonian through a phase-space surface hopping (PSSH) algorithm employing a pseudo-diabatic basis. Here, we show that such a pseudo-diabatic PSSH (PD-PSSH)…

Quantum Physics · Physics 2023-01-25 Yanze Wu , Joseph Subotnik

A new approximate solution to the quantum-classical Liouville equation is derived starting from the formal solution of this equation in forward-backward form. The time evolution of a mixed quantum-classical system described by this equation…

Chemical Physics · Physics 2015-06-05 Chang-Yu Hsieh , Raymond Kapral

In this article we show how Ehrenfest mean field theory can be made both a more accurate and efficient method to treat nonadiabatic quantum dynamics by combining it with the generalized quantum master equation framework. The resulting mean…

Chemical Physics · Physics 2015-06-23 Aaron Kelly , Nora Brackbill , Thomas E. Markland

We present an approach for carrying out non-adiabatic molecular dynamics simulations of systems in which non-adiabatic transitions arise from the coupling between the classical atomic motions and a quasi-continuum of electronic quantum…

Computational Physics · Physics 2018-11-21 Jerome Daligault , Dmitry Mozyrsky

Chemical relaxation phenomena, including photochemistry and electron transfer processes, form a vigorous area of research in which nonadiabatic dynamics plays a fundamental role. Here, we show that for nonadiabatic dynamics with two…

Chemical Physics · Physics 2022-07-20 Yanze Wu , Xuezhi Bian , Jonathan Rawlinson , Robert G. Littlejohn , Joseph E. Subotnik

We implement a rare-event sampling scheme for quantifying the rate of thermally-activated nonadiabatic transitions in the condensed phase. Our QM/MM methodology uses the recently developed INAQS package to interface between an elementary…

Chemical Physics · Physics 2023-03-23 Alec J. Coffman , Zuxin Jin , Junhan Chen , Joseph E. Subotnik , D. Vale Cofer-Shabica

In open quantum systems decoherence occurs through interaction of a quantum subsystem with its environment. The computation of expectation values requires a knowledge of the quantum dynamics of operators and sampling from initial states of…

Statistical Mechanics · Physics 2009-11-13 Robbie Grunwald , Hyojoon Kim , Raymond Kapral

Nonadiabatic dynamics methods are an essential tool for investigating photochemical processes. In the context of employing first principles electronic structure techniques, such simulations can be carried out in a practical manner using…

Chemical Physics · Physics 2024-05-08 Jonathan R. Mannouch , Aaron Kelly

Nonadiabatic molecular dynamics is a key technique for investigating a broad range of photochemical and photophysical processes. Among the established approaches, surface hopping schemes are widely used and can be easily integrated with…

Chemical Physics · Physics 2025-12-23 Jakub Martinka , Mikołaj Martyka , Biman Medhi , Jiří Pittner , Pavlo O. Dral

We propose a nonadiabatic approach to quantum annealing, in which we repeat quantum annealing in nonadiabatic time scales, and collect the final states of many realizations to find the ground state among them. In this way, we replace the…

Statistical Mechanics · Physics 2013-03-26 Hitoshi Katsuda , Hidetoshi Nishimori

We carried out extensive studies to examine the performance of the fewest-switches surface hopping method in the description of the ultrafast intersystem crossing dynamic of various singlet-triplet (S-T) models by comparison with the…

Chemical Physics · Physics 2019-05-22 Jiawei Peng , Yu Xie , Deping Hu , Zhenggang Lan

The powerful molecular dynamics (MD) simulation is basically based on a picture that the atoms experience classical-like trajectories under the exertion of classical force field determined by the quantum mechanically solved electronic…

Chemical Physics · Physics 2013-12-16 Wei Feng , Luting Xu , Xin-Qi Li , Weihai Fang

Mixed quantum-classical methods provide powerful algorithms for the simulation of quantum processes in large and complex systems. The forward-backward trajectory solution of the mixed quantum-classical Liouville equation in the mapping…

Chemical Physics · Physics 2015-06-15 Chang-Yu Hsieh , Raymond Kapral
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