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We present a preliminary surface-hopping approach for modeling intersystem crossing (ISC) dynamics between four electronic states: one singlet and one (triply degenerate) triplet. In order to incorporate all Berry force effects, the…

Chemical Physics · Physics 2022-03-29 Xuezhi Bian , Yanze Wu , Hung-Hsuan Teh , Joseph E. Subotnik

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 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

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

Non-adiabatic chemical reactions involving continuous circularly polarized light (cw CPL) have not attracted as much attention as dynamics in unpolarized/linearly polarized light. However, including circularly (in contrast to linearly)…

Chemical Physics · Physics 2022-09-20 Zeyu Zhou , Yanze Wu , Xuezhi Bian , Joseph Eli Subotnik

A new scheme is proposed for modeling molecular nonadiabatic dynamics near metal surfaces. The charge-transfer character of such dynamics is exploited to construct an efficient reduced representation for the electronic structure. In this…

Chemical Physics · Physics 2020-09-24 Zuxin Jin , Joseph E. Subotnik

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 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

A new methodology of simulating nonadiabatic dynamics using frozen-width Gaussian wavepackets within the moving crude adiabatic representation with the on-the-fly evaluation of electronic structure is presented. The main feature of the new…

Chemical Physics · Physics 2018-04-04 Loïc Joubert-Doriol , Artur F. Izmaylov

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

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

We propose an approximate method for evaluating the importance of non-Born-Oppenheimer effects on the quantum dynamics of nuclei. The method uses a generalization of the dephasing representation (DR) of quantum fidelity to several diabatic…

Chemical Physics · Physics 2013-01-15 Tomas Zimmermann , Jiri Vanicek

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

Ring Polymer Surface-Hopping (RPSH) has been recently introduced as a well-tailored method for incorporating nuclear quantum effects (NQEs), such as zero-point energy and tunneling, into non-adiabatic molecular dynamics simulations. The…

Chemical Physics · Physics 2025-09-16 Dil K. Limbu , Farnaz A. Shakib

Trajectory surface hopping (TSH) is one of the most widely used quantum-classical algorithms for nonadiabatic molecular dynamics. Despite its empirical effectiveness and popularity, a rigorous derivation of TSH as the classical limit of a…

Chemical Physics · Physics 2013-01-11 J. M. Escartín , P. Romaniello , L. Stella , P. -G. Reinhard , E. Suraud

We develop a Floquet surface hopping (FSH) approach to deal with nonadiabatic dynamics of molecules near metal surfaces subjected to time-periodic drivings from strong light-matter interactions. The method is based on a Floquet classical…

Quantum Physics · Physics 2023-06-21 Yu Wang , Wenjie Dou

The diagonal Born-Oppenheimer correction (DBOC) stems from the diagonal second derivative coupling term in the adiabatic representation, and it can have an arbitrary large magnitude when a gap between neighbouring Born-Oppenheimer (BO)…

Chemical Physics · Physics 2016-05-02 Rami Gherib , Liyuan Ye , Ilya G. Ryabinkin , Artur F. Izmaylov

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

On-the-fly quantum nonadiabatic dynamics for large systems greatly benefits from the adiabatic representation readily available from the electronic structure programs. However, frequently occurring in this representation conical…

We consider a system with spin-orbit coupling and derive equations of motion which include the effects of Berry curvatures. We apply these equations to investigate the dynamics of particles with equal Rashba-Dresselhaus spin-orbit coupling…

Quantum Gases · Physics 2017-04-19 J. Armaitis , J. Ruseckas , E. Anisimovas
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