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We describe a path-integral approach for including nuclear quantum effects in non-adiabatic chemical dynamics simulations. For a general physical system with multiple electronic energy levels, a corresponding isomorphic Hamiltonian is…

Statistical Mechanics · Physics 2018-06-05 Xuecheng Tao , Philip Shushkov , Thomas Miller

Chemical relaxation phenomena, including photochemistry and electron transfer processes, form a vigorous area of research in which nonadiabatic dynamics plays a fundamental role. Here, we show that for nonadiabatic dynamics with two…

Chemical Physics · Physics 2022-07-20 Yanze Wu , Xuezhi Bian , Jonathan Rawlinson , Robert G. Littlejohn , Joseph E. Subotnik

The interaction between electronic and vibrational degrees of freedom is an important mechanism in nonequilibrium charge transport through molecular nanojunctions. While adiabatic polaron-type coupling has been studied in great detail, new…

Mesoscale and Nanoscale Physics · Physics 2022-06-10 Christoph Kaspar , André Erpenbeck , Jakob Bätge , Christian Schinabeck , Michael Thoss

We prove that for a combined system of classical and quantum particles, it is possible to write a dynamics for the classical particles that incorporates in a natural way the Boltzmann equilibrium population for the quantum subsystem. In…

Other Condensed Matter · Physics 2010-09-01 J. L. Alonso , A. Castro , P. Echenique , V. Polo , A. Rubio , D. Zueco

Molecular dynamics (MD) simulation based on Langevin equation has been widely used in the study of structural, thermal properties of matters in difference phases. Normally, the atomic dynamics are described by classical equations of motion…

Mesoscale and Nanoscale Physics · Physics 2018-02-06 Jing-Tao Lü , Bing-Zhong Hu , Per Hedegård , Mads Brandbyge

Based on a semi-empirical generalized Anderson-Newns model we construct a pseudo-particle description for electron emission due to de-excitation of metastable molecules at surfaces. The pseudo-particle approach allows us to treat resonant…

Strongly Correlated Electrons · Physics 2015-06-05 Johannes Marbach , Franz Xaver Bronold , Holger Fehske

A general theoretical framework is derived for the recently developed multi-state trajectory (MST) approach from the time dependent Schr\"odinger equation, resulting in equations of motion for coupled nuclear-electronic dynamics equivalent…

Chemical Physics · Physics 2017-09-13 Guohua Tao

We derive an explicit form for the electronic friction as felt by a molecule near a metal surface for the general case that molecule-metal couplings depend on nuclear coordinates. Our work generalizes a previous study by von Oppen et al…

Chemical Physics · Physics 2016-11-23 Wenjie Dou , Joseph E. Subotnik

We build on the concept of eigenvector continuation to develop an efficient multi-state method for the rigorous and smooth interpolation of a small training set of many-body wavefunctions through chemical space at mean-field cost. The…

Chemical Physics · Physics 2024-05-02 Kemal Atalar , Yannic Rath , Rachel Crespo-Otero , George H. Booth

The quantum dynamics of a subset of interacting bosons in a subspace of fixed particle number is described in terms of symmetrized many-particle states. A suitable partial trace operation over the von Neumann equation of an $N$-particle…

Quantum Physics · Physics 2018-02-21 Manuel Gessner , Andreas Buchleitner

We examine time-resolved X-ray diffraction from molecules in the gas phase which undergo nonadiabatic avoided-crossing dynamics involving strongly coupled electrons and nuclei. Several contributions to the signal are identified,…

Chemical Physics · Physics 2017-05-30 Markus Kowalewski , Kochise Bennett , Shaul Mukamel

Transition metal complexes for photochemical applications often feature a high density of electron-vibrational states characterized by nonadiabatic and spin-orbit couplings. Overall, the dynamics after photoexcitation is shaped by rapid…

Chemical Physics · Physics 2023-05-16 Olga Bokareva , Oliver Kühn

Trajectory-based mixed quantum-classical approaches to coupled electron-nuclear dynamics suffer from well-studied problems such as the lack of (or incorrect account for) decoherence in the trajectory surface hopping method and the inability…

Quantum Physics · Physics 2016-02-29 Federica Agostini , Seung Kyu Min , Ali Abedi , E. K. U. Gross

Geometric phases play a crucial role in diverse fields. In chemistry they appear when a reaction path encircles an intersection between adiabatic potential energy surfaces and the molecular wavefunction experiences quantum-mechanical…

Quantum Physics · Physics 2024-02-05 Rocco Martinazzo , Irene Burghardt

Incorporating nuclear quantum effects into nonadiabatic dynamics remains a significant challenge. Herein we introduce new nonadiabatic dynamics approaches based on the recently developed constrained nuclear-electronic orbital (CNEO) theory.…

Chemical Physics · Physics 2025-04-15 Zhe Liu , Zehua Chen , Yang Yang

An approach to correlated dynamics of quantum nuclei and electrons both in dynamical interaction with external environments is presented. This stochastic quantum molecular dynamics rests on a theorem that establishes a one-to-one…

Materials Science · Physics 2012-12-27 Heiko Appel , Massimiliano Di Ventra

We present a comprehensive computational framework for simulating nonadiabatic molecular dynamics with explicit inclusion of geometric phase (GP) effects. Our approach is based on a generalized two-level Hamiltonian model that can represent…

Mesoscale and Nanoscale Physics · Physics 2025-10-17 Dhruv Sharma

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

Dinuclear systems that occur in the post-saddle to scission stage in nuclear fission process are special transient formations. The diabatic evolution at this stage is studied using the methods of non-equilibrium thermodynamics. A novel…

Nuclear Theory · Physics 2023-05-01 Bency John

While the treatment of conical intersections in molecular dynamics generally requires nonadiabatic approaches, the Born-Oppenheimer adiabatic approximation is still adopted as a valid alternative in certain circumstances. In the context of…

Chemical Physics · Physics 2020-09-16 Jonathan I. Rawlinson , Cesare Tronci