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In this article, we propose a Frozen Gaussian Sampling (FGS) algorithm for simulating nonadiabatic quantum dynamics at metal surfaces with a continuous spectrum. This method consists of a Monte-Carlo algorithm for sampling the initial wave…

Computational Physics · Physics 2022-11-30 Zhen Huang , Limin Xu , Zhennan Zhou

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

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, 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 propose a method which combines the quantum-classical mapping approach to surface hopping (MASH) with the dissipative quantum dynamics of the Lindblad master equation. Like conventional surface-hopping methods, our approach is based on…

Quantum Physics · Physics 2026-03-31 Kasra Asnaashari , Jeremy O. Richardson

This paper provides the first ab-initio on-the-fly example of using the Quasi-Diabatic (QD) scheme for non-adiabatic simulations with diabatic dynamics approaches. The QD scheme provides a seamless interface between diabatic quantum…

Computational Physics · Physics 2019-08-15 Wanghuai Zhou , Arkajit Mandal , Pengfei Huo

Accurate description of nonadiabatic dynamics of molecules at metal surfaces involving electron transfer has been a longstanding challenge for theory. Here, we tackle this problem by first constructing high-dimensional neural network…

Materials Science · Physics 2024-01-05 Gang Meng , James Gardner , Wenjie Dou , Reinhard J. Maurer , Bin Jiang

We report an implementation for employing the algebraic diagrammatic construction to second order [ADC(2)] ab initio electronic structure level of theory in nonadiabatic dynamics simulations in the framework of the SHARC (surface hopping…

Chemical Physics · Physics 2019-01-11 Sebastian Mai , Felix Plasser , Mathias Pabst , Frank Neese , Andreas Köhn , Leticia González

Non-adiabatic dynamics simulations have become a standard approach to explore photochemical reactions. Such simulations require underlying potential energy surfaces and couplings between them, calculated at a chosen level of theory, yet…

Chemical Physics · Physics 2024-05-28 Thomas V. Papineau , Denis Jacquemin , Morgane Vacher

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

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

Nonadiabatic dynamical processes are one of the most important quantum mechanical phenomena in chemical, materials, biological, and environmental molecular systems, where the coupling between different electronic states is either inherent…

Chemical Physics · Physics 2022-05-24 Jian Liu , Xin He , Baihua Wu

Nonadiabatic molecular dynamics simulations aim to describe the coupled electron-nuclear dynamics of molecules in excited electronic states. These simulations have been applied to understand a plethora of photochemical and photophysical…

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 propose a trajectory-based method for simulating nonadiabatic dynamics in molecular systems with two coupled electronic states. Employing a quantum-mechanically exact mapping of the two-level problem to a spin-1/2 coherent state, we…

Chemical Physics · Physics 2020-03-03 Johan E. Runeson , Jeremy O. Richardson

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

Nonadiabatic coupling between electrons and molecular motion at metal surfaces leads to energy dissipation and dynamical steering effects during chemical surface dynamics. We present a theoretical approach to the scattering of molecules…

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

We introduce an improved semiclassical dynamics approach to quantum vibrational spectroscopy. In this method, a harmonic-based phase space sampling is preliminarily driven toward non-harmonic quantization by slowly switching on the actual…

Chemical Physics · Physics 2019-12-09 Riccardo Conte , Lorenzo Parma , Chiara Aieta , Alessandro Rognoni , Michele Ceotto

We present an approach for carrying out non-adiabatic molecular dynamics simulations of systems in which non-adiabatic transitions arise from the coupling between the classical atomic motions and a quasi-continuum of electronic quantum…

Computational Physics · Physics 2018-11-21 Jerome Daligault , Dmitry Mozyrsky