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We develop a multi-state generalisation of the recently proposed mapping approach to surface hopping (MASH) for the simulation of electronically nonadiabatic dynamics. This new approach extends the original MASH method to be able to treat…

Chemical Physics · Physics 2024-03-19 Joseph E. Lawrence , Jonathan R. Mannouch , Jeremy O. Richardson

A novel quantum dynamical method to simulate vibronic reaction dynamics in molecules at metal surfaces is proposed. The method is based on the hierarchical quantum master equation approach and uses a discrete variable representation of the…

Chemical Physics · Physics 2019-12-05 A. Erpenbeck , M. Thoss

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

We present a novel semiclassical phase-space surface hopping approach that goes beyond the Born-Oppenheimer approximation and all existing surface hopping formalisms. We demonstrate that working with a correct phase-space electronic…

Chemical Physics · Physics 2024-10-03 Xuezhi Bian , Yanze Wu , Tian Qiu , Tao Zhen , Joseph E. Subotnik

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 surface hopping algorithm based on frozen Gaussian approximation for semiclassical matrix Schr\"odinger equations, in the spirit of Tully's fewest switches surface hopping method. The algorithm is asymptotically derived from…

Numerical Analysis · Mathematics 2017-03-30 Jianfeng Lu , Zhennan Zhou

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

Non-adiabatic molecular dynamics (NAMD) has become an essential computational technique for studying the photophysical relaxation of molecular systems after light absorption. These phenomena require approximations that go beyond the…

We propose a novel algorithm for the approximation of surface-quasi geostrophic (SQG) flows modeled by a nonlinear partial differential equation coupling transport and fractional diffusion phenomena. The time discretization consists of an…

Numerical Analysis · Mathematics 2020-06-03 Andrea Bonito , Murtazo Nazarov

The exact factorization approach has led to the development of new mixed quantum-classical methods for simulating coupled electron-ion dynamics. We compare their performance for dynamics when more than two electronic states are occupied at…

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

Fewest-switches surface hopping (FSSH) has emerged as one of the leading methods for modeling the quantum dynamics of molecular systems. While its original formulation was limited to adiabatic populations, the growing interest in the…

Chemical Physics · Physics 2023-02-22 Anna S. Bondarenko , Roel Tempelaar

Nuclear Berry curvature effects emerge from electronic spin degeneracy and canlead to non-trivial spin-dependent (nonadiabatic) nuclear dynamics. However, such effects are completely neglected in all current mixed quantum-classical methods…

Chemical Physics · Physics 2022-08-29 Xuezhi Bian , Yanze Wu , Jonathan Rawlinson , Robert G. Littlejohn , Joseph E. Subotnik

The Exact Factorization (XF) of molecular wavefunctions can be viewed as an 'electronic wavepacket' framework for quantum dynamics. It is an appealing alternative to the conventional non-adiabatic dynamics, unfolding in the space of coupled…

Chemical Physics · Physics 2025-10-10 Julian Stetzler , Sophya Garashchuk , Vitaly A. Rassolov

Interest in vibrational polaritonic chemistry, where ground-state chemical kinetics are modified via confined optical modes in a cavity, has surged in recent years. Although models have been developed to understand cavity-modified…

Quantum Physics · Physics 2025-02-10 Muhammad R. Hasyim , Arkajit Mandal , David R. Reichman

Nonadiabatic quantum interferences emerge whenever nuclear wavefunctions in different electronic states meet and interact in a nonadiabatic region. In this work, we analyze how nonadiabatic quantum interferences translate in the context of…

Chemical Physics · Physics 2016-08-03 Basile F. E. Curchod , Federica Agostini , E. K. U. Gross

A semicalssical method based on surface-hopping techniques is developed to model the dynamics of radiative association with electronic transitions in arbitrary polyatomic systems. It can be proven that our method is an extension of the…

Chemical Physics · Physics 2017-10-11 Péter Szabó , Magnus Gustafsson

We present an efficient \textit{ab initio} algorithm for quantum dynamics simulations of interacting systems that is based on the conditional decomposition of the many-body wavefunction [Phys. Rev. Lett. 113, 083003 (2014)]. Starting with…

Mesoscale and Nanoscale Physics · Physics 2019-02-27 Guillermo Albareda , Aaron Kelly , Angel Rubio

In this work, we employ trajectory-based simulations to predict the electronic coherences created by nonadiabatic dynamics near conical intersections. The mapping approach to surface hopping (MASH) is compared with standard fewest-switches…

Chemical Physics · Physics 2025-05-09 Daniele Furlanetto , Jeremy O. Richardson

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