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Born-Oppenheimer dynamics is shown to provide an accurate approximation of time-independent Schr\"odinger observables for a molecular system with an electron spectral gap, in the limit of large ratio of nuclei and electron masses, without…

Mathematical Physics · Physics 2011-09-21 Christian Bayer , Håkon Hoel , Petr Plecháč , Anders Szepessy , Raúl Tempone

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

We report on highly accurate calculations of Born-Oppenheimer potentials for excited $n\,\Sigma^{+}$ states of the hydrogen molecule for all possible combinations of singlet/triplet and gerade/ungerade symmetries up to $n=7$. A relative…

Atomic Physics · Physics 2023-02-28 Michał Siłkowski , Magdalena Zientkiewicz , Krzysztof Pachucki

We report on accurate variational calculations of the Born-Oppenheimer potential for excited states of the hydrogen molecule with $\Pi$, $\Delta$, and $\Phi$ symmetries. The obtained potential energy curves reach the relative precision of…

Atomic Physics · Physics 2023-01-11 Michał Siłkowski , Krzysztof Pachucki

The essence of atomic structure theory, quantum chemistry, and computational materials science is solving the multi-electron stationary Schr\"odinger equation. The Quantum Monte Carlo-based neural network wave function method has surpassed…

Atomic Physics · Physics 2023-12-27 JinDe Liu , Chenglong Qin , Xi He , Gang Jiang

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

The energies of molecular excited states arise as solutions to the electronic Schr\"{o}dinger equation and are often compared to experiment. At the same time, nuclear quantum motion is known to be important and to induce a red-shift of…

Chemical Physics · Physics 2021-06-28 Timothy J. H. Hele , Bartomeu Monserrat , Antonios M. Alvertis

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

At non-zero temperature and when a system has low-lying excited electronic states, the ground-state Born--Oppenheimer approximation breaks down and the low-lying electronic states are involved in any chemical process. In this work, we use a…

Chemical Physics · Physics 2012-09-07 J. L. Alonso , A. Castro , J. Clemente-Gallardo , P. Echenique , J. J. Mazo , V. Polo , A. Rubio , D. Zueco

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…

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

Quantum-classical molecular dynamics, as a partial classical limit of the full quantum Schr\"odinger equation, is a widely used framework for quantum molecular dynamics. The underlying equations are nonlinear in nature, containing a quantum…

Numerical Analysis · Mathematics 2023-01-25 Di Fang , Albert Tres

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

In the present paper an example of entanglement between two different kinds of interacting particles, photons and electrons is analysed. The initial-value problem of the Schroedinger equation is solved non-perturbatively for the system of a…

Quantum Physics · Physics 2010-10-05 Sandor Varro

Excited states of molecules lie in the heart of photochemistry and chemical reactions. The recent development in quantum computational chemistry leads to inventions of a variety of algorithms that calculate the excited states of molecules…

Quantum Physics · Physics 2020-11-05 Hiroki Kawai , Yuya O. Nakagawa

This paper is a continuation of a previous work about the study of the survival probability modelizing the molecular predissociation in the Born-Oppenheimer framework. Here we consider the critical case where the reference energy…

Mathematical Physics · Physics 2018-12-21 Philippe Briet , André Martinez

The role of electron-nuclear entanglement on the validity of the Born-Oppenheimer (BO) approximation is investigated. While nonadiabatic couplings generally lead to entanglement and to a failure of the BO approximation, surprisingly the…

Quantum Physics · Physics 2016-05-24 Artur F. Izmaylov , Ignacio Franco

Approximating ground and a fixed number of excited state energies, or equivalently low order Hamiltonian eigenvalues, is an important but computationally hard problem. Typically, the cost of classical deterministic algorithms grows…

Quantum Physics · Physics 2015-08-10 Stuart Hadfield , Anargyros Papageorgiou

Electronically excited states of molecules are at the heart of photochemistry, photophysics, as well as photobiology and also play a role in material science. Their theoretical description requires highly accurate quantum chemical…

Chemical Physics · Physics 2021-03-15 Julia Westermayr , Philipp Marquetand
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