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Laser-induced molecular alignment is well understood within the framework of the Born-Oppenheimer (BO) approximation Without the BO approximation, however, the concept of molecular structure is lost, making alignment hard to define…

Chemical Physics · Physics 2022-09-16 Ludwik Adamowicz , Simen Kvaal , Caroline Lasser , Thomas Bondo Pedersen

We review techniques for simulating fully quantum nonadiabatic dynamics using the frozen-width moving Gaussian basis functions to represent the nuclear wavefunction. A choice of these basis functions is primarily motivated by the idea of…

Chemical Physics · Physics 2018-09-05 Loïc Joubert-Doriol , Artur F. Izmaylov

Quantum computing has the potential to reduce the computational cost required for quantum dynamics simulations. However, existing quantum algorithms for coupled electron-nuclear dynamics simulation either require fault-tolerant devices, or…

Quantum Physics · Physics 2026-03-03 Jong-Kwon Ha , Ryan J. MacDonell

We present a universal expression for the electronic friction as felt by a set of classical nuclear degrees of freedom (DoF's) coupled to a manifold of quantum electronic DoF's; no assumptions are made regarding the nature of the electronic…

Materials Science · Physics 2017-08-02 Wenjie Dou , Gaohan Miao , Joseph E. Subotnik

The Born-Oppenheimer approximation leads to the counterintuitive result of a vanishing electronic flux density upon vibrational dynamics in the electronic ground state. To circumvent this long known issue, we propose using pairwise…

Quantum Physics · Physics 2016-04-26 Vincent Pohl , Jean Christophe Tremblay

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

The coupling of electronic and nuclear motion in polyatomic molecules is at the heart of attochemistry. The molecular properties, transient structures and reaction mechanism of these many-body quantum objects are defined on the level of…

Chemical Physics · Physics 2024-03-12 David Schwickert , Andreas Przystawik , Dian Diaman , Detlef Kip , Jon P. Marangos , Tim Laarmann

A theory of electronic friction is developed using the exact factorization of the electron-nuclear wavefunction. No assumption is made regarding the electronic bath, which can be made of independent or interacting electrons, and the nuclei…

Quantum Physics · Physics 2022-06-01 Rocco Martinazzo , Irene Burghardt

Direct dynamics methods using Gaussian wavepackets have to rely only on local properties, such as gradients and hessians at the center of the wavepacket, so as to be compatible with the usual quantum chemistry methods. Matrix elements of…

Chemical Physics · Physics 2016-04-26 Alexander Humeniuk , Roland Mitric

We analyze the entanglement between electronic and nuclear motions in molecular wave functions, by using different widely used ansatzes in molecular Hamiltonian models (H$^+_2$ in 1D and the Shin-Metiu model); namely, i) Born-Oppenheimer…

Quantum Physics · Physics 2025-11-13 Juan F. P. Mosquera , Jose Luis Sanz-Vicario

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

A new methodology of simulating nonadiabatic dynamics using frozen-width Gaussian wavepackets within the moving crude adiabatic representation with the on-the-fly evaluation of electronic structure is presented. The main feature of the new…

Chemical Physics · Physics 2018-04-04 Loïc Joubert-Doriol , Artur F. Izmaylov

Exposing a molecule to intense light pulses may bring this molecule to a nonstationary quantum state, thus launching correlated dynamics of electronic and nuclear subsystems. Although much had been achieved in the understanding of…

Chemical Physics · Physics 2024-04-11 Nikolay V. Golubev , Jiří Vaníček

Quantum molecular dynamics requires an accurate representation of the molecular potential energy surface from a minimal number of electronic structure calculations, particularly for nonadiabatic dynamics where excited states are required.…

Chemical Physics · Physics 2016-08-24 Charles W. Heaps , David A. Mazziotti

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…

A precise understanding of mechanisms governing the dynamics of electrons in atoms and molecules subjected to intense laser fields has a key importance for the description of attosecond processes such as the high-harmonic generation and…

Within the nuclear-electronic orbital (NEO) framework, the real-time NEO time-dependent density functional theory (RT-NEO-TDDFT) approach enables the simulation of coupled electronic-nuclear dynamics. In this approach, the electrons and…

Chemical Physics · Physics 2023-03-22 Tao E. Li , Sharon Hammes-Schiffer

Photoionization using attosecond pulses can lead to the formation of coherent superpositions of the electronic states of the parent ion. However, ultrafast electron ejection triggers not only electronic but also nuclear dynamics---leading…

Chemical Physics · Physics 2017-03-29 Caroline Arnold , Oriol Vendrell , Robin Santra

We revisit the three-body problem in quantum mechanics in two and three dimensions, generating both exact eigenvalues and eigenvectors of the Hamiltonian and a series of approximate solutions as calculated with a variety of different…

We develop a formalism to accurately account for the renormalization of electronic structure due to quantum and thermal nuclear motions within the Born-Oppenheimer approximation. We focus on the fundamental energy gap obtained from…

Materials Science · Physics 2021-02-03 Vitaly Gorelov , David M. Ceperley , Markus Holzmann , Carlo Pierleoni
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