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We compute the ab-initio electron density beyond the strict Born-Oppenheimer approximation in crystalline LiH and LiD with density functional methods. By taking into account the quantum mechanical nature of the nuclei, an aspect absent in…

Materials Science · Physics 2026-03-13 Ville J. Härkönen

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 phase-space electronic structure theory of molecules in magnetic fields. For a system of electrons in a magnetic field with vector potential $\bf{A}(\hat{\bf{r}})$, the usual Born-Oppenheimer Hamiltonian is the sum of the…

Chemical Physics · Physics 2024-11-25 Mansi Bhati , Zhen Tao , Xuezhi Bian , Jonathan Rawlinson , Robert Littlejohn , Joseph E. Subotnik

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

We introduce a general technique to compute finite temperature electronic properties by a novel covariant formulation of the electronic partition function. By using a rigorous variational upper bound to the free energy we are led to the…

Strongly Correlated Electrons · Physics 2013-06-19 Guglielmo Mazzola , Andrea Zen , Sandro Sorella

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

A generalized approach of the Born-Oppenheimer approximation is developed to analytically deal with the influence exercised by the spatial motion of atom's mass-center on a two-level atom in an optical ring cavity with a quantized…

High Energy Physics - Theory · Physics 2007-05-23 Chang-Pu Sun

Quantum trajectory calculations for electrons are a useful tool in the field of molecular dynamics, e.g. to understand processes in ultrafast spectroscopy. They have, however, two limitation: On the one hand, such calculations are typically…

Chemical Physics · Physics 2021-09-29 Axel Schild

Graph-based linear scaling electronic structure theory for quantum-mechanical molecular dynamics simulations is adapted to the most recent shadow potential formulations of extended Lagrangian Born-Oppenheimer molecular dynamics, including…

Chemical Physics · Physics 2023-03-08 Christian F. A. Negre , Michael E. Wall , Anders M. N. Niklasson

Hydrogen has been the subject of intense research following the discovery of high-temperature superconductivity in hydrides, and as a result of continuous efforts to produce solid hydrogen. The Born-Oppenheimer approximation is the central…

Materials Science · Physics 2023-11-13 Ville J. Härkönen

In recent years, there has been a push to go beyond Born-Oppenheimer theory and build electronic states from a phase space perspective, i.e. parameterize electronic states by both nuclear position(R) and nuclear momentum(P). Previous…

Chemical Physics · Physics 2025-06-11 Xinchun Wu , Xuezhi Bian , Jonathan Rawlinson , Robert G. Littlejohn , Joseph E. Subotnik

We introduce an efficient scheme for the molecular dynamics of electronic systems by means of quantum Monte Carlo. The evaluation of the (Born-Oppenheimer) forces acting on the ionic positions is achieved by two main ingredients: i) the…

Strongly Correlated Electrons · Physics 2007-05-23 Sandro Sorella , Claudio Attaccalite

Experiments have demonstrated that vibrational strong coupling between molecular vibrations and light modes can significantly change molecular properties, such as ground-state reactivity. Theoretical studies towards the origin of this…

Chemical Physics · Physics 2024-01-09 Marit R. Fiechter , Jeremy O. Richardson

The total energy is a fundamental characteristic of solids, molecules, and nanostructures. In most first-principles calculations of the total energy, the nuclear kinetic operator is decoupled from the many-body electronic Hamiltonian and…

Materials Science · Physics 2026-02-17 Samuel Poncé , Xavier Gonze

Using the Wentzel-Kramers-Brillouin method, we derive a modified form of the Thomas-Fermi approximation to electron density. This new result enables us to calculate the details of the self-consistent ion cores, as well as the ionization…

Materials Science · Physics 2009-02-23 Gregory C. Dente , Michael L. Tilton

The Born--Oppenheimer approximation is the standard tool for the study of molecular systems. It is founded on the observation that the energy scale of the electron dynamics in a molecule is larger than that of the nuclei. A very similar…

High Energy Physics - Phenomenology · Physics 2018-01-31 Nora Brambilla , Gastão Krein , Jaume Tarrús Castellà , Antonio Vairo

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 present a novel theory and implementation for computing coupled electronic and quantal nuclear subsystems on a single potential energy surface, moving beyond the standard Born-Oppenheimer (BO) separation of nuclei and electrons. We…

Chemical Physics · Physics 2021-11-15 Ziyong Chen , Jun Yang

We show that a phase space electronic Hamiltonian $\hat{H}_{PS}(\mathbf{X},\mathbf{P})$, parameterized by both nuclear position $\mathbf{X}$ and momentum $\mathbf{P}$, can recover not just experimental vibrational circular dichroism (VCD)…

In this work, we illustrate the recently introduced concept of the cavity Born-Oppenheimer approximation for correlated electron-nuclear-photon problems in detail. We demonstrate how an expansion in terms of conditional electronic and…

Quantum Physics · Physics 2017-04-12 Johannes Flick , Heiko Appel , Michael Ruggenthaler , Angel Rubio
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