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Ehrenfest, Born-Oppenheimer, Langevin and Smoluchowski dynamics are shown to be accurate approximations of time-independent Schr\"odinger observables for a molecular system avoiding caustics, in the limit of large ratio of nuclei and…

Mathematical Physics · Physics 2010-01-12 Anders Szepessy

In this paper, we consider the time-dependent Born-Oppenheimer approximation (BOA) of a classical quantum molecule involving a possibly large number of nuclei and electrons, described by a Schr\"odinger equation. In the spirit of Born and…

Quantum Physics · Physics 2025-05-27 Sebastian Gherghe , Iván Moyano , Israel Michael Sigal

We present the construction of an exponentially accurate time-dependent Born-Oppenheimer approximation for molecular quantum mechanics. We study molecular systems whose electron masses are held fixed and whose nuclear masses are…

Mathematical Physics · Physics 2009-10-31 George A. Hagedorn , Alain Joye

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

Describing the dynamics of nuclei in molecules requires a potential energy surface, which is traditionally provided by the Born-Oppenheimer or adiabatic approximation. However, we also need to assign masses to the nuclei. There, the…

We formulate a time-dependent density functional theory for the coupled dynamics of electrons and nuclei that goes beyond the Born-Oppenheimer (BO) approximation. We prove that the time-dependent marginal nuclear probability density…

Chemical Physics · Physics 2025-11-14 Chen Li , Ryan Requist , E. K. U. Gross

The molecular Schr\"odinger equation is rewritten in terms of non-unitary equations of motion for the nuclei (or electrons) that depend parametrically on the configuration of an ensemble of generally defined electronic (or nuclear)…

Mesoscale and Nanoscale Physics · Physics 2016-02-18 Guillermo Albareda , Heiko Appel , Ignacio Franco , Ali Abedi , Angel Rubio

We analyze the time reversible Born-Oppenheimer molecular dynamics (TRBOMD) scheme, which preserves the time reversibility of the Born-Oppenheimer molecular dynamics even with non-convergent self-consistent field iteration. In the linear…

Numerical Analysis · Mathematics 2015-06-16 Lin Lin , Jianfeng Lu , Sihong Shao

The local conservation of a physical quantity whose distribution changes with time is mathematically described by the continuity equation. The corresponding time parameter, however, is defined with respect to an idealized classical clock.…

Chemical Physics · Physics 2018-11-21 Axel Schild

In our previous paper [J. Chem.Phys. {\bf 137}, 22A544 (2012)] we argued that the Born-Oppenheimer approximation could not be based on an exact transformation of the molecular Schr\"{o}dinger equation. In this Comment we suggest that the…

Quantum Physics · Physics 2015-06-18 Brian T Sutcliffe , R Guy Woolley

Stochastic Schr\"odinger equations that govern the dynamics of open quantum systems are given by the equations for signal processing. In particular, the Brownian motion that drives the wave function of the system does not represent noise,…

Biological Physics · Physics 2022-09-28 Dorje C. Brody

Solving the electronic Schr\"odinger equation for changing nuclear coordinates provides access to the Born-Oppenheimer potential energy surface. This surface is the key starting point for almost all theoretical studies of chemical processes…

Chemical Physics · Physics 2022-01-14 Markus Reiher

Extended Lagrangian Born-Oppenheimer molecular dynamics [Phys. Rev. Lett., ${\bf 100}$, 123004 (2008)] is formulated for general Hohenberg-Kohn density functional theory and compared to the extended Lagrangian framework of first principles…

Materials Science · Physics 2017-09-13 Anders M. N. Niklasson

We present an improved field-theoretic approach to the grand-canonical potential suitable for linear scaling molecular dynamics simulations using forces from self-consistent electronic structure calculations. It is based on an exact…

Computational Physics · Physics 2014-06-23 Dorothee Richters , Thomas D. Kühne

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

Electronic decoherence processes in molecules and materials are usually thought and modeled via schemes for the system-bath evolution in which the bath is treated either implicitly or approximately. Here we present computations of the…

Chemical Physics · Physics 2018-04-18 Wenxiang Hu , Bing Gu , Ignacio Franco

In pre-Born-Oppenheimer (pre-BO) theory a molecule is considered as a quantum system as a whole, including the electrons and the atomic nuclei on the same footing. This approach is fundamentally different from the traditional quantum…

Chemical Physics · Physics 2019-02-20 Edit Matyus

We present a time-reversible Born-Oppenheimer molecular dynamics scheme, based on self-consistent Hartree-Fock or density functional theory, where both the nuclear and the electronic degrees of freedom are propagated in time. We show how a…

Materials Science · Physics 2009-11-11 Anders M. N. Niklasson , C. J. Tymczak , Matt Challacombe

Molecular dynamics refers to the computer simulation of a material at the atomic level. An open problem in numerical analysis is to explain the apparent reliability of molecular dynamics simulations. The difficulty is that individual…

Numerical Analysis · Mathematics 2015-05-13 P. F. Tupper

Extended Lagrangian Born-Oppenheimer molecular dynamics based on Kohn-Sham density functional theory is generalized in the limit of vanishing self-consistent field optimization prior to the force evaluations. The equations of motion are…

Chemical Physics · Physics 2015-06-23 Anders M. N. Niklasson , Marc J. Cawkwell
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