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A surface-hopping algorithm recently derived from the exact factorization approach, SHXF, [Ha, Lee, Min, J. Phys. Chem. Lett. 9, 1097 (2018)] introduces an additional term in the electronic equation of surface-hopping, which couples…

Chemical Physics · Physics 2022-02-08 Patricia Vindel-Zandbergen , Spiridoula Matsika , Neepa T. Maitra

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

We present a detailed study of the decoherence correction to surface-hopping that was recently derived from the exact factorization approach. Ab initio multiple spawning calculations that use the same initial conditions and same electronic…

For a system without spin-orbit coupling, the (i) nuclear plus electronic linear momentum and (ii) nuclear plus orbital electronic angular momentum are good quantum numbers. Thus, when a molecular system undergoes a nonadiabatic transition,…

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

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

Modeling the dynamics of non-bound states in molecules requires an accurate description of how electronic motion affects nuclear motion and vice-versa. The exact factorization (XF) approach offers a unique perspective, in that it provides…

Chemical Physics · Physics 2022-05-16 Evaristo Villaseco Arribas , Federica Agostini , Neepa T. Maitra

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

The exact factorization of the time-dependent electron-nuclear wavefunction has been employed successfully in the field of quantum molecular dynamics simulations for interpreting and simulating light-induced ultrafast processes. In this…

Chemical Physics · Physics 2021-09-29 Federica Agostini , E. K. U. Gross

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

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

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

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

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

Intersystem crossing is a radiationless process that can take place in a molecule irradiated by UV-Vis light, thereby playing an important role in many environmental, biological and technological processes. This paper reviews different…

Chemical Physics · Physics 2017-03-29 Sebastian Mai , Philipp Marquetand , Leticia González

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

We address the issues of decoherence, frustrated hops and internal consistency in surface hopping. We demonstrate that moving away from an independent-trajectory picture is the strategy which allows us to propose a robust surface hopping…

Chemical Physics · Physics 2025-09-01 Lea M. Ibele , Eduarda Sangiogo Gil , Peter Schürger , Rodrigue Noc , Federica Agostini

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

Independent electron surface hopping (IESH) is a computational algorithm for simulating the mixed quantum-classical molecular dynamics of adsorbate atoms and molecules interacting with metal surfaces. It is capable of modelling the…

Chemical Physics · Physics 2023-02-22 James Gardner , Daniel Corken , Svenja M. Janke , Scott Habershon , Reinhard J. Maurer

We perform on-the-fly non-adiabatic molecular dynamics simulations using the symmetrical quasi-classical (SQC) approach with the recently suggested molecular Tully models: ethylene and fulvene. We attempt to provide benchmarks of the SQC…

Chemical Physics · Physics 2021-09-15 Braden M. Weight , Arkajit Mandal , Pengfei Huo
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