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We present a rare event sampling scheme applicable to coupled electronic excited states. In particular, we extend the forward flux sampling (FFS) method for rare event sampling to a nonadiabatic version (NAFFS) that uses the trajectory…

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

Aluminum nanocrystals offer a promising platform for plasmonic photocatalysis, yet a detailed understanding of their electron dynamics and consequent photocatalytic performance has been challenging thus far due to computational limitations.…

Mesoscale and Nanoscale Physics · Physics 2025-04-29 Nikhil S. Chellam , George C. Schatz

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

We introduce a novel methodology for simulating the excited-state dynamics of extensive molecular aggregates in the framework of the long-range corrected time-dependent density-functional tight-binding fragment molecular orbital method…

Chemical Physics · Physics 2024-04-23 Richard Einsele , Roland Mitrić

Density Functional Tight Binding (DFTB) is an attractive method for accelerated quantum simulations of condensed matter due to its enhanced computational efficiency over standard Density Functional Theory approaches. However, DFTB models…

While surface-hopping has emerged as a powerful method to simulate non-adiabatic dynamics in large molecules, the ad hoc nature of the necessary velocity adjustments and decoherence corrections in the algorithm somewhat reduces its…

Chemical Physics · Physics 2024-01-17 Lucien Dupuy , Anton Rikus , Neepa T. Maitra

Screened range-separated hybrid (SRSH) functionals within generalized Kohn-Sham density functional theory (GKS-DFT) have been shown to restore a general $1/(r\varepsilon)$ asymptotic decay of the electrostatic interaction in dielectric…

Computational Physics · Physics 2023-06-26 Tammo van der Heide , Bálint Aradi , Ben Hourahine , Thomas Frauenheim , Thomas A. Niehaus

Nonadiabatic couplings (NACs) play a crucial role in modeling photochemical and photophysical processes with methods such as the widely used fewest-switches surface hopping (FSSH). There is therefore a strong incentive to machine learn NACs…

Computational Physics · Physics 2026-03-17 Jakub Martinka , Lina Zhang , Yi-Fan Hou , Mikołaj Martyka , Jiří Pittner , Mario Barbatti , Pavlo O. Dral

A surface-adsorbed molecule is contacted with the tip of a scanning tunneling microscope (STM) at a pre-defined atom. On tip retraction, the molecule is peeled off the surface. During this experiment, a two-dimensional differential…

Mesoscale and Nanoscale Physics · Physics 2024-01-30 C. Toher , R. Temirov , A. Greuling , F. Pump , M. Kaczmarski , M. Rohlfing , G. Cuniberti , F. S. Tautz

Vibrational dynamics of adsorbates near surfaces plays both an important role for applied surface science and as model lab for studying fundamental problems of open quantum systems. We employ a previously developed model for the relaxation…

Chemical Physics · Physics 2022-07-01 Eric W. Fischer , Michael Werther , Foudhil Bouakline , Frank Grossmann , Peter Saalfrank

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

The applicability of the density functional based tight binding (DFTB) method to the description of hydrogen bond dynamics and infrared spectroscopy is addressed for the exemplary protic ionic liquid triethylammonium nitrate. Potential…

Chemical Physics · Physics 2017-01-04 Tobias Zentel , Oliver Kühn

Fewest-switches surface hopping (FSSH) is the most popular method for simulating photochemical processes of molecular systems. Recently, we have constructed long short-term memory (LSTM) networks as a propagator for electronic subsystems in…

Chemical Physics · Physics 2026-05-25 Zhenxing Zhu , Diandong Tang , Lin Shen , Wei-Hai Fang

Analogue Hamiltonian simulation (AHS) in photonic systems can be an enticing alternative to direct experimental study of complex Hamiltonian systems as a result of the low cost and high degree of control one can have over the system's…

Optics · Physics 2026-01-12 Nathaniel Fried , Dashiell L. P. Vitullo , Avik Dutt

Current neural networks for predictions of molecular properties use quantum chemistry only as a source of training data. This paper explores models that use quantum chemistry as an integral part of the prediction process. This is done by…

Chemical Physics · Physics 2018-08-22 Haichen Li , Christopher Collins , Matteus Tanha , Geoffrey J. Gordon , David J. Yaron

A software package, called DFTBaby, is published, which provides the electronic structure needed for running non-adiabatic molecular dynamics simulations at the level of charge-consistent tight-binding DFT. A long-range correction is…

Chemical Physics · Physics 2017-10-25 Alexander Humeniuk , Roland Mitric

In this work, we describe various improved implementations of the mapping approach to surface hopping (MASH) for simulating nonadiabatic dynamics. These include time-reversible and piecewise-continuous integrators, which is only formally…

Chemical Physics · Physics 2026-03-31 J. Amira Geuther , Kasra Asnaashari , Jeremy O. Richardson

Two-dimensional (2D) materials exhibit a wide range of electronic properties that make them promising candidates for next-generation nanoelectronic devices. Accurate prediction of their quantum transport behavior is therefore of both…

Materials Science · Physics 2025-12-22 Jijie Zou , Zhanghao Zhouyin , Qiangqiang Gu , Shishir Kumar Pandey

The transient time correlation function method (TTCF) has emerged as a powerful methodology for accurately probing systems at low shear rates. In the present study, TTCF was used to evaluate the shear rate dependence of the slip length in a…

Chemical Physics · Physics 2026-03-24 Carmelo Civello , Luca Maffioli , Edward Smith , James Ewen , Peter Daivis , Daniele Dini , Billy Todd