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Mixed-quantum-classical molecular dynamics simulation implies an effective measurement on the electronic states owing to continuously tracking the atomic forces.Based on this insight, we propose a quantum trajectory mean-field approach for…

Chemical Physics · Physics 2014-08-08 Wei Feng , Luting Xu , Xin-Qi Li , Weihai Fang , YiJing Yan

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

Efficient sampling from high-dimensional distributions is a challenging issue which is encountered in many large data recovery problems involving Markov chain Monte Carlo schemes. In this context, sampling using Hamiltonian dynamics is one…

Methodology · Statistics 2015-02-02 Lotfi Chaari , Jean-Yves Tourneret , Caroline Chaux , Hadj Batatia

The theoretical investigation of non-adiabatic processes is hampered by the complexity of the coupled electron-nuclear dynamics beyond the Born-Oppenheimer approximation. Classically, the simulation of such reactions is limited by the…

Quantum Physics · Physics 2021-01-06 Pauline J. Ollitrault , Guglielmo Mazzola , Ivano Tavernelli

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

In this paper, we apply multi-task Gaussian Process (MT-GP) to show that the adsorption energy of small adsorbates on transition metal surfaces can be modeled to a high level of fidelity using data from multiple sources, taking advantage of…

Data Analysis, Statistics and Probability · Physics 2019-01-29 Huijie Tian , Srinivas Rangarajan

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

We propose an optimization algorithm called Frictionless Hamiltonian Descent, which is a direct counterpart of classical Hamiltonian Monte Carlo in sampling. We analyze Frictionless Hamiltonian Descent for strongly convex quadratic…

Optimization and Control · Mathematics 2026-02-26 Jun-Kun Wang

Dissociative chemisorption is a key process in hydrogen-metal surface chemistry, where nonadiabatic effects due to low-lying electron-hole-pair excitations may affect reaction outcomes. Molecular dynamics with electronic friction…

Chemical Physics · Physics 2025-05-26 Wojciech G. Stark , Connor L. Box , Matthias Sachs , Nils Hertl , Reinhard J. Maurer

The stochastic-gauge representation is a method of mapping the equation of motion for the quantum mechanical density operator onto a set of equivalent stochastic differential equations. One of the stochastic variables is termed the…

Quantum Physics · Physics 2010-11-02 Mark R. Dowling , Matthew J. Davis , Peter D. Drummond , Joel F. Corney

The dynamics of spin-boson systems at very low temperatures has been studied using a real-time path-integral simulation technique which combines a stochastic Monte Carlo sampling over the quantum fluctuations with an exact treatment of the…

chem-ph · Physics 2009-10-22 Reinhold Egger , C. H. Mak

We derive and implement analytic nuclear gradients and derivative couplings for a constrained Complete Active Space Self-Consistent Field with a small active space designed to model electron or hole transfer. Using a Lagrangian formalism,…

Computational Physics · Physics 2025-09-01 Tian Qiu , Joseph E. Subotnik

Non-adiabatic dynamics at molecule-metal interfaces govern diverse and technologically important phenomena, from heterogeneous catalysis to dye-sensitized solar energy conversion and charge transport across molecular junctions. Realistic…

Quantum Physics · Physics 2026-02-27 Robert A. Lang , Paarth Jain , Juan Miguel Arrazola , Danial Motlagh

Continuous-time quantum Monte Carlo refers to a class of algorithms designed to sample the thermal distribution of a quantum Hamiltonian through exact expansions of the Boltzmann exponential in terms of stochastic trajectories which are…

Statistical Mechanics · Physics 2024-07-17 Luke Causer , Konstantinos Sfairopoulos , Jamie F. Mair , Juan P. Garrahan

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

Accurate simulation of the non-adiabatic dynamics of molecules in excited electronic states is key to understanding molecular photo-physical processes. Here we present a novel method, based on a semiclassical approximation, that is as…

Chemical Physics · Physics 2016-05-24 Alexander White , Sergei Tretiak , Dmitry Mozyrsky

We propose digitized counterdiabatic quantum sampling (DCQS), a hybrid quantum-classical algorithm for efficient sampling from energy-based models, such as low-temperature Boltzmann distributions. The method utilizes counterdiabatic…

We perform extensive benchmark comparisons of surface hopping dynamics with numerically exact calculations for the spin-boson model over a wide range of energetic and coupling parameters as well as temperature. We find that deviations from…

Mesoscale and Nanoscale Physics · Physics 2016-04-04 Hsing-Ta Chen , David R. Reichman

This article presents a rigorous analysis for efficient statistically accurate algorithms for solving the Fokker-Planck equations associated with high-dimensional nonlinear turbulent dynamical systems with conditional Gaussian structures.…

Statistics Theory · Mathematics 2017-09-19 Nan Chen , Andrew J. Majda , Xin T. Tong

The so-called phaseless quantum Monte-Carlo method currently offers one of the best performing theoretical framework to investigate interacting Fermi systems. It allows to extract an approximate ground-state wavefunction by averaging…

Strongly Correlated Electrons · Physics 2017-03-31 Olivier Juillet , Alexandre Leprévost , Jérémy Bonnard , Raymond Frésard