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Akin to the traditional quasi-classical trajectory method for investigating the dynamics on a single adiabatic potential energy surface for an elementary chemical reaction, we carry out the dynamics on a 2-state ab initio potential energy…

Vibrational energies and wave functions of the triplet state of the H3+ ion have been determined. In the calculations, the ground and first excited triplet electronic states are included as well as the non-Born-Oppenheimer coupling between…

Chemical Physics · Physics 2016-05-25 Alexander Alijah , Viatcheslav Kokoouline

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

The coupling of electronic and vibrational motion is studied by two canonical transformations namely normal coordinate transformation and momentum transformation on molecular Hamiltonian. It is shown that by these transformations we can…

Chemical Physics · Physics 2007-05-23 Ivan Hubac , Peter Babinec , Martin Polasek , Jan Urban , Pavel Mach , Jozef Masik , Jerzy Leszczynski

We present a novel nonadiabatic perturbation theory (NAPT) for correlated systems of electrons and nuclei beyond the Born-Oppenheimer (BO) approximation. The essence of the method is to exploit the smallness of the electronic-to-nuclear…

Chemical Physics · Physics 2025-11-05 Matisse Wei-Yuan Tu , E. K. U. Gross

An adiabatic approach is developed for the problem of boundary friction between two atomically smooth and incommensurate solid surfaces, separated by a monolayer of lubricant atoms. This method permits to consider very slow macroscopic…

Materials Science · Physics 2007-05-23 Yu. G. Pogorelov

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

Electronic friction and Langevin dynamics is a popular mixed quantum-classical method for simulating the nonadiabatic dynamics of molecules interacting with metal surfaces, as it can be computationally more efficient than fully quantum…

Chemical Physics · Physics 2024-06-06 Martin Mäck , Samuel L. Rudge , Michael Thoss

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 present explicit form of non-adiabatic coupling (NAC) elements of nuclear Schroedinger equation (SE) for a coupled tri-state electronic manifold in terms of mixing angles of real electronic basis functions. If the adiabatic-diabatic…

Chemical Physics · Physics 2007-05-23 Biplab Sarkar , Satrajit Adhikari

An accurate description of electron-ion interactions in materials is crucial for our understanding of their equilibrium and non-equilibrium properties. Here, we assess the properties of frictional forces experienced by ions in…

Disordered Systems and Neural Networks · Physics 2020-07-15 Jacopo Simoni , Jerome Daligault

Dynamical fluctuations in classical adiabatic processes are not considered by the conventional classical adiabatic theorem. In this work a general result is derived to describe the intrinsic dynamical fluctuations in classical adiabatic…

Classical Physics · Physics 2012-02-10 Qi Zhang , Jiangbin Gong , C. H. Oh

The interaction between electronic and vibrational degrees of freedom in single-molecule junctions may result from the dependence of the electronic energies or the electronic states of the molecular bridge on the nuclear displacement. The…

Mesoscale and Nanoscale Physics · Physics 2015-06-09 A. Erpenbeck , R. Härtle , M. Thoss

Nonadiabatic corrections in molecules composed of a few atoms are considered. It is demonstrated that a systematic perturbative expansion around the adiabatic solution is possible, with the expansion parameter being the electron-nucleus…

Chemical Physics · Physics 2009-11-13 Krzysztof Pachucki , Jacek Komasa

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

We present the theory for the evaluation of non-adiabatic couplings (NACs) involving resonance states within the complex absorbing potential equation-of-motion coupled-cluster (CAP-EOM-CC) framework implemented within the singles and…

For classical Hamiltonian systems, the adiabatic condition may fail at some critical points. However, the breakdown of the adiabatic condition does not always make the adiabatic evolution be destroyed. In this paper, we suggest a…

Classical Physics · Physics 2009-11-11 Li-Bin Fu , Shi-Gang Chen

Nonadiabatic molecular dynamics (NAMD) is widely used to describe hot electron relaxation and nonradiative recombination processes, but high computational costs limit its application to large supercells. Here, we implement a nonadiabatic…

Chemical Physics · Physics 2026-05-26 Xiaoke He , Hsiao-Yi Tsai , Ziwei Chai , Junwen Yin , Zhongfei Xu , Li-Min Liu

This report presents a new approach for treating the coupling of electrons and nuclei in quantum mechanical calculations for molecules and condensed matter. It includes the standard "Born-Oppenheimer approximation" as a special case but…

Chemical Physics · Physics 2013-06-28 Gerald I. Kerley

An approach to non-adiabatic dynamics of atoms in molecular and condensed matter systems under general non-equilibrium conditions is proposed. In this method interaction between nuclei and electrons is considered explicitly up to the second…

Materials Science · Physics 2018-08-01 L. Kantorovich
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