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Surface hopping algorithms are popular tools to study dynamics of the quantum-classical mixed systems. In this paper, we propose a surface hopping algorithm in diabatic representations, based on time dependent perturbation theory and…

Numerical Analysis · Mathematics 2022-10-19 Di Fang , Jianfeng Lu

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

A class of surface hopping algorithms is studied comparing two recent Landau-Zener (LZ) formulas for the probability of nonadiabatic transitions. One of the formulas requires a diabatic representation of the potential matrix while the other…

Chemical Physics · Physics 2015-06-19 Andrey K. Belyaev , Caroline Lasser , Giulio Trigila

The quantum-classical Liouville equation offers a rigorous approach to nonadiabatic quantum dynamics based on surface hopping type trajectories. However, in practice the applicability of this approach has been limited to short times owing…

Chemical Physics · Physics 2015-06-16 Aaron Kelly , Thomas E. Markland

We investigate a simple and robust scheme for choosing the phases of adiabatic electronic states smoothly (as a function of geometry) so as to maximize the performance of ab initio non-adiabatic dynamics methods. Our approach is based upon…

Chemical Physics · Physics 2019-09-26 Zeyu Zhou , Zuxin Jin , Tian Qiu , Andrew M. Rappe , Joseph Eli Subotnik

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

It is well known that fewest-switches surface hopping (FSSH) fails to correctly capture the quadratic scaling of rate constants with diabatic coupling in the weak-coupling limit, as expected from Fermi's golden rule and Marcus theory. To…

Chemical Physics · Physics 2023-11-16 Joseph E. Lawrence , Jonathan R. Mannouch , Jeremy O. Richardson

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

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

At present, several models for quantum computation have been proposed. Adiabatic quantum computation scheme particularly offers this possibility and is based on a slow enough time evolution of the system, where no transitions take place. In…

Quantum Physics · Physics 2012-10-12 P. J. Salas Peralta

In the spirit of the fewest switches surface hopping, the frozen Gaussian approximation with surface hopping (FGA-SH) method samples a path integral representation of the non-adiabatic dynamics in the semiclassical regime. An improved…

Chemical Physics · Physics 2016-10-12 Jianfeng Lu , Zhennan Zhou

Marcus--Hush theory explains electron transfer in terms of reorganization energies, driving forces, electronic couplings, and reduced free-energy or energy-gap descriptions. These descriptions do not by themselves determine when the…

Chemical Physics · Physics 2026-05-19 Stephen Wiggins

Recently, the mapping approach to surface hopping (MASH) was proposed as a method to simulate the non-adiabatic dynamics of two-level systems. It was shown that the method possesses many desirable qualities, both theoretically and through…

Chemical Physics · Physics 2025-07-08 Jan Vavřín

This paper provides the first ab-initio on-the-fly example of using the Quasi-Diabatic (QD) scheme for non-adiabatic simulations with diabatic dynamics approaches. The QD scheme provides a seamless interface between diabatic quantum…

Computational Physics · Physics 2019-08-15 Wanghuai Zhou , Arkajit Mandal , Pengfei Huo

We perform extensive benchmark comparisons of surface hopping dynamics with numerically exact calculations for the spin-boson model over a wide range of energetic and coupling parameters as well as temperature. We find that deviations from…

Mesoscale and Nanoscale Physics · Physics 2016-04-04 Hsing-Ta Chen , David R. Reichman

Adiabatic optimal control schemes are essential for advancing the practical implementation of quantum technologies. However, the vast array of possible adiabatic protocols, combined with their dependence on the particular quantum system and…

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

An extension of the CCS-method [Chem. Phys. 2004, 304, p. 103-120] for simulating non-adiabatic dynamics with quantum effects of the nuclei is put forward. The time-dependent Schr\"{o}dinger equation for the motion of the nuclei is solved…

Chemical Physics · Physics 2016-07-27 Alexander Humeniuk , Roland Mitrić

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

The crossover from nonadiabatic to adiabatic electron transfer has been theoretically studied under a spin-boson model (dissipative two-state system) description. We present numerically exact data for the thermal transfer rate and the…

Condensed Matter · Physics 2009-11-07 L. Muehlbacher , R. Egger
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