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We present in detail the recently derived ab-initio molecular dynamics (AIMD) formalism [Phys. Rev. Lett. 101 096403 (2008)], which due to its numerical properties, is ideal for simulating the dynamics of systems containing thousands of…

A new "on the fly" method to perform Born-Oppenheimer ab initio molecular dynamics (AIMD) is presented. Inspired by Ehrenfest dynamics in time-dependent density functional theory, the electronic orbitals are evolved by a Schroedinger-like…

We present a new method which combines Car-Parrinello and Born-Oppenheimer molecular dynamics in order to accelerate density functional theory based ab-initio simulations. Depending on the system a gain in efficiency of one to two orders of…

Materials Science · Physics 2007-05-23 Thomas D. Kühne , Matthias Krack , Fawzi R. Mohamed , Michele Parrinello

Mixed quantum-classical mechanics descriptions are critical to modeling coupled electron-nuclear dynamics, i.e. non-adiabatic molecular dynamics, relevant to photochemical and photophysical processes. We argue that, for polyatomic…

Chemical Physics · Physics 2018-08-21 Roman Baskov , Alexander White , Dmitry Mozyrsky

Computer simulation methods, such as Monte Carlo or Molecular Dynamics, are very powerful computational techniques that provide detailed and essentially exact information on classical many-body problems. With the advent of ab-initio…

Chemical Physics · Physics 2014-06-23 Thomas D. Kühne

The dynamics of an electronic system interacting with an electromagnetic field is investigated within mixed quantum-classical theory. Beyond the classical path approximation (where we ignore all feedback from the electronic system on the…

Chemical Physics · Physics 2019-02-11 Hsing-Ta Chen , Tao E. Li , Maxim Sukharev , Abraham Nitzan , Joseph E. Subotnik

We have derived equations for nonadiabatic Ehrenfest molecular dynamics which conserve the total energy in the case of time-dependent discretization for electrons. A discretization is time-dependent in all cases where it or part of it…

Materials Science · Physics 2015-05-30 Ari Ojanperä , Ville Havu , Lauri Lehtovaara , Martti Puska

Density functional theory with linear combination of atomic orbitals (LCAO) basis sets is useful for studying large atomic systems, especially when it comes to computationally highly demanding time-dependent dynamics. We have implemented…

Materials Science · Physics 2025-05-02 Vladimír Zobač , Mikael Kuisma , Ask Hjorth Larsen , Tuomas Rossi , Toma Susi

This paper describes a method to do ab initio molecular dynamics in electronically excited systems within the random phase approximation (RPA). Using a dynamical variational treatment of the RPA frequency, which corresponds to the…

Condensed Matter · Physics 2009-10-31 Eric R. Bittner , D. S. Kosov

The Ehrenfest dynamics, representing a quantum-classical mean-field type coupling, is a widely used approximation in quantum molecular dynamics. In this paper, we propose a time-splitting method for an Ehrenfest dynamics, in the form of a…

Numerical Analysis · Mathematics 2022-10-19 Di Fang , Shi Jin , Christof Sparber

One key challenge in the study of nonadiabatic dynamics in open quantum systems is to balance computational efficiency and accuracy. Although Ehrenfest dynamics (ED) is computationally efficient and well-suited for large complex systems, ED…

Quantum Physics · Physics 2024-12-02 Jingqi Chen , Joonho Lee , Wenjie Dou

The difference of the values of observables for the time-independent Schroedinger equation, with matrix valued potentials, and the values of observables for ab initio Born-Oppenheimer molecular dynamics, of the ground state, depends on the…

Numerical Analysis · Mathematics 2015-05-13 Christian Bayer , Hakon Hoel , Ashraful Kadir , Petr Plechac , Mattias Sandberg , Anders Szepessy

Simulating electron-ion dynamics using time-dependent density functional theory within an Ehrenfest dynamics scheme can be done in two ways that are in principle exact and identical: propagating time-dependent electronic Kohn-Sham equations…

Chemical Physics · Physics 2021-07-01 Lionel Lacombe , Neepa T. Maitra

Second-generation Car--Parrinello \textit{ab initio} molecular dynamics (CP2G AIMD) combines a Born--Oppenheimer-like nuclear equation of motion with a predictor-corrector propagation of the one-particle density matrix and a modified…

Computational Physics · Physics 2026-05-26 Thomas D. Kühne

We propose an adaptive random quantum algorithm to obtain an optimized eigensolver. Specifically, we introduce a general method to parametrize and optimize the probability density function of a random number generator, which is the core of…

We present a formalism that explicitly unifies the commonly used Nakajima-Zwanzig approach for reduced density matrix dynamics with the more versatile Mori theory in the context of nonequilibrium dynamics. Employing a Dyson-type expansion…

Chemical Physics · Physics 2016-05-25 Andrés Montoya-Castillo , David. R. Reichman

We discuss the evolution of purity in mixed quantum/classical approaches to electronic nonadiabatic dynamics in the context of the Ehrenfest model. As it is impossible to exactly determine initial conditions for a realistic system, we…

Chemical Physics · Physics 2012-09-07 J. L. Alonso , J. Clemente-Gallardo , J. C. Cuchí , P. Echenique , F. Falceto

This article shows a proof of concept regarding the feasibility of ab initio molecular simulation, wherein the wavefunctions and the positions of nuclei are simultaneously determined by the quantum algorithm, as is realized by the so-called…

Quantum Physics · Physics 2025-04-23 Ichio Kikuchi , Akihito Kikuchi

We benchmark a set of quantum-chemistry methods, including multitrajectory Ehrenfest, fewest-switches surface-hopping, and multiconfigurational-Ehrenfest dynamics, against exact quantum-many-body techniques by studying real-time dynamics in…

Due to a continuum of electronic states present in periodic systems, the description of molecular dynamics on surfaces poses a serious computational challenge. One of the most used families of approaches in these settings are friction…

Chemical Physics · Physics 2021-12-08 Ignacio Loaiza , Artur F. Izmaylov
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