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We present a detailed derivation and numerical tests of a new mixed quantum-classical scheme to deal with non-adiabatic processes. The method is presented as the zero-th order approximation to the exact coupled dynamics of electrons and…

Chemical Physics · Physics 2015-06-22 Federica Agostini , Ali Abedi , E. K. U. Gross

Nonadiabatic dynamics methods are an essential tool for investigating photochemical processes. In the context of employing first principles electronic structure techniques, such simulations can be carried out in a practical manner using…

Chemical Physics · Physics 2024-05-08 Jonathan R. Mannouch , Aaron Kelly

The accuracy of the noninteracting electron approximation is examined for a model of vibrationally coupled electron transport in single molecule junction. In the absence of electronic-vibrational coupling, steady state transport in this…

Mesoscale and Nanoscale Physics · Physics 2017-01-04 Haobin Wang , Michael Thoss

Ehrenfest dynamics is a useful approximation for ab initio mixed quantum-classical molecular dynamics that can treat electronically nonadiabatic effects. Although a severe approximation to the exact solution of the molecular time-dependent…

Chemical Physics · Physics 2021-09-24 Seonghoon Choi , Jiří Vaníček

Most microscopic descriptions of structural dynamics assume the Born-Oppenheimer separation, where electrons adjust adiabatically to ionic motion. When this separation breaks down, electronic and lattice degrees of freedom can evolve on…

Materials Science · Physics 2026-02-26 Gili Scharf , Lara Donval , Leah Ben Gur , Alon Ron

A first-principles coupled electron-nuclear dynamics simulation based on real-time, time-dependent density functional theory and Ehrenfest dynamics quantitatively repro-duces bimodal translational energy loss and angular distributions…

Chemical Physics · Physics 2025-12-05 Jialong Shi , Lingjun Zhu , Florian Nitz , Oliver Bünermann , Alec M. Wodtke , Hua Guo , Bin Jiang

The choice of the electronic representation in on-the-fly quantum dynamics is crucial. The adiabatic representation is appealing since adiabatic states are readily available from quantum chemistry packages. The nuclear wavepackets are then…

Chemical Physics · Physics 2022-05-03 Rosa Maskri , Loïc Joubert-Doriol

The powerful molecular dynamics (MD) simulation is basically based on a picture that the atoms experience classical-like trajectories under the exertion of classical force field determined by the quantum mechanically solved electronic…

Chemical Physics · Physics 2013-12-16 Wei Feng , Luting Xu , Xin-Qi Li , Weihai Fang

To understand the recently observed mysterious non-adiabatic energy transfer for hyperthermal H atom scattering from a semiconductor surface, Ge(111)c(2*8), we present a mixed quantum-classical non-adiabatic molecular dynamics model based…

This article deals with non-adiabatic processes (i.e. processes excluded by the adiabatic theorem) from the geometrical (group-theoretical) point of view. An approximated formula for the probabilities of the non-adiabatic transitions is…

Quantum Physics · Physics 2009-11-06 M. S. Marinov , E. Strahov

An approach to the quantum-classical mechanics of phase space dependent operators, which has been proposed recently, is remodeled as a formalism for wave fields. Such wave fields obey a system of coupled non-linear equations that can be…

Quantum Physics · Physics 2007-05-23 Alessandro Sergi

We present a general multi-component density functional theory in which electrons and nuclei are treated completely quantum mechanically, without the use of a Born-Oppenheimer approximation. The two fundamental quantities in terms of which…

Materials Science · Physics 2007-05-23 Thomas Kreibich , Robert van Leeuwen , E. K. U. Gross

A novel treatment of non-adiabatic couplings is proposed. The derivation starts from the long-known, but not well-known, fact that the wave function of the complete system of elctrons and nuclei can be written, without approximation, as a…

Materials Science · Physics 2007-05-23 Nikitas I. Gidopoulos , E. K. U. Gross

This article presents an alternative formulation of quasi-degenerate perturbation theory (QDPT). The development results by simplifying established many-body (MB) techniques to systems of non-interacting particles (NIP). While the physical…

Chemical Physics · Physics 2023-09-28 Jochen Schirmer

Nonadiabatic quantum interferences emerge whenever nuclear wavefunctions in different electronic states meet and interact in a nonadiabatic region. In this work, we analyze how nonadiabatic quantum interferences translate in the context of…

Chemical Physics · Physics 2016-08-03 Basile F. E. Curchod , Federica Agostini , E. K. U. Gross

We present a self-contained theoretical and computational framework for dynamics following photoexcitation in quantum dots near planar interfaces. A microscopic Hamiltonian parameterized by first principles calculations is merged with a…

Mesoscale and Nanoscale Physics · Physics 2015-06-15 Kuljit S. Virk , Mark S. Hybertsen , David R. Reichman

Diabatization of the molecular Hamiltonian is a standard approach to removing the singularities of nonadiabatic couplings at conical intersections of adiabatic potential energy surfaces. In general, it is impossible to eliminate the…

Chemical Physics · Physics 2021-03-26 Seonghoon Choi , Jiří Vaníček

The ever-growing intersection of quantum electrodynamics (QED) and molecular processes has shown remarkable and unanticipated advancements in altering molecular properties and reactivity by exploiting light-matter couplings. In recent…

Chemical Physics · Physics 2023-11-09 Xinyang Li , Yu Zhang

Electron transfer is an important and fundamental process in chemistry, biology and physics, and has received significant attention in recent years. Perhaps one of the most intriguing questions concerns with the realization of the…

Mesoscale and Nanoscale Physics · Physics 2023-05-30 Bokang Hou , Michael Thoss , Uri Banin , Eran Rabani

Starting with the exact factorization of the molecular wavefunction, this paper presents the results from the numerical implementation in nonadiabatic molecular dynamics of the recently proposed bohmion method. Within the context of quantum…

Chemical Physics · Physics 2021-10-06 Darryl D. Holm , Jonathan I. Rawlinson , Cesare Tronci