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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 novel mixed quantum-classical approach to simulating nonadiabatic dynamics of molecules at metal surfaces is presented. The method combines the numerically exact hierarchical equations of motion approach for the quantum electronic degrees…

Mesoscale and Nanoscale Physics · Physics 2024-05-06 Samuel L. Rudge , Christoph Kaspar , Robin L. Grether , Steffen Wolf , Gerhard Stock , Michael Thoss

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

We propose to measure nonadiabaticity of molecular quantum dynamics rigorously with the quantum fidelity between the Born-Oppenheimer and fully nonadiabatic dynamics. It is shown that this measure of nonadiabaticity applies in situations…

Chemical Physics · Physics 2012-06-28 Tomas Zimmermann , Jiri Vanicek

In the study of non-adiabatic chemical processes such as photocatalysis and photosynthesis, non-adiabatic molecular dynamics (NAMD) is an indispensable theoretical tool, which requires precise potential energy surfaces (PESs) of ground and…

Chemical Physics · Physics 2026-01-19 Tianyi Li , Yumeng Zeng , Qiming Ding , Zixuan Huo , Xiaosi Xu , Jiajun Ren , Diandong Tang , Xiaoxia Cai , Xiao Yuan

We present a highly efficient method to directly simulate the photodissociation followed by Coulomb explosion of methyl iodide. In order to achieve statistical reliability, more than 40,000 trajectories are calculated on accurate potential…

Chemical Physics · Physics 2024-11-06 Yijue Ding , Loren Greenman , Daniel Rolles

We propose an 'automatic' approach to analyze the results of the on-the-fly trajectory surface hopping simulation on the multi-channel nonadiabatic photoisomerization dynamics by considering the trajectory similarity and the configuration…

Chemical Physics · Physics 2019-01-30 Xusong Li , Deping Hu , Yu Xie , Zhenggang Lan

Nonadiabatic ring-polymer molecular dynamics employs the mapping approach to describe nonadiabatic effects within the ring-polymer ansatz. In this paper, it is generalized to allow for the nuclear and electronic degrees of freedom to be…

Chemical Physics · Physics 2017-08-23 Jeremy O. Richardson , Philipp Meyer , Marc-Oliver Pleinert , Michael Thoss

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 adiabatic quantum computing the aim is to track an eigenstate as the Hamiltonian changes. In the usual setup this is achieved using the natural time-dependent Hamiltonian evolution of the system and the main technical tool is the…

Quantum Physics · Physics 2026-05-29 Joseph Cunningham , Jérémie Roland

Quantum computation is an attractive front for many problems that are intractable for computers today. One such problem is nonadiabatic quantum molecular dynamics, where quantized internal states coupling to parameterized modes result in a…

Quantum Physics · Physics 2026-04-22 Joshua Courtney

In the paper we derive a semiclassical model for surface hopping allowing quantum dynamical non-adiabatic transition between different potential energy surfaces in which cases the classical Born-Oppenheimer approximation breaks down. The…

Numerical Analysis · Mathematics 2014-05-06 Lihui Chai , Shi Jin , Qin Li , Omar Morandi

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

Designing proper time-dependent control fields for slowly varying the system to the ground state that encodes the problem solution is crucial for adiabatic quantum computation. However, inevitable perturbations in real applications demand…

Quantum Physics · Physics 2020-07-22 Xiaodong Yang , Ran Liu , Jun Li , Xinhua Peng

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

We present a new partially linearized mapping-based approach for approximating real-time quantum correlation functions in condensed-phase nonadiabatic systems, called spin-PLDM. Within a classical trajectory picture, partially linearized…

Chemical Physics · Physics 2021-02-03 J. R. Mannouch , J. O. Richardson

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…

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

Nonadiabatic molecular dynamics offers a powerful tool for studying the photochemistry of molecular systems. Key to any nonadiabatic molecular dynamics simulation is the definition of its initial conditions, ideally representing the initial…

Chemical Physics · Physics 2023-09-08 Antonio Prlj , Daniel Hollas , Basile F. E. Curchod

A major challenge in nonadiabatic molecular dynamics is to automatically and objectively identify the key reaction coordinates that drive molecules toward distinct excited-state decay channels. Traditional manual analyses are inefficient…

Chemical Physics · Physics 2025-11-18 Hangxu Liu , Yifei Zhu , Zhenggang Lan