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Nuclear quantum effects and non-Born--Oppenheimer effects play a vital role in many chemical and biological processes, motivating the incorporation of such effects into dynamical simulations. In real-time nuclear--electronic orbital…

Chemical Physics · Physics 2026-05-27 Nicholas J. Boyer , Sharon Hammes-Schiffer

The Born-Oppenheimer (BO) approximation is less accurate in the presence of a strong magnetic field than in the absence of a field. This is due to the complicated and unpredictable response of electronic structure to the field, especially…

Chemical Physics · Physics 2023-03-29 Tanner Culpitt , Laurens D. M. Peters , Erik I. Tellgren , Trygve Helgaker

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

Nuclear quantum phenomena beyond the Born-Oppenheimer approximation are known to play an important role in a growing number of chemical and biological processes. While there exists no unique consensus on a rigorous and efficient…

Nuclear quantum effects such as zero-point energy and hydrogen tunnelling play a central role in many biological and chemical processes. The nuclear-electronic orbital (NEO) approach captures these effects by treating selected nuclei…

The nuclear-electronic orbital (NEO) method is a well-established approach for treating nuclei quantum mechanically in molecular systems beyond the usual Born-Oppenheimer approximation. In this work, we present a strategy to implement the…

Computational Physics · Physics 2022-06-29 Jianhang Xu , Ruiyi Zhou , Zhen Tao , Christopher Malbon , Volker Blum , Sharon Hammes-Schiffer , Yosuke Kanai

Plasmonic nanocavities are a promising platform for strong light-matter coupling and enhanced spectroscopies at the single-molecule level. These nanoscale environments are challenging to model due to their strongly multimodal character and…

Chemical Physics · Physics 2026-03-16 Jonathan H. Fetherolf , Tao E. Li , Sharon Hammes-Schiffer

The computational investigation of photochemical processes often entails the calculation of excited state geometries, energies, and energy gradients. The nuclear-electronic orbital (NEO) approach treats specified nuclei, typically protons,…

We present a Lagrangian-based implementation of Ehrenfest dynamics with nuclear-electronic orbital (NEO) theory and real-time time-dependent density functional theory (RT-TDDFT) for extended periodic systems. In addition to a quantum…

Chemical Physics · Physics 2024-07-29 Jianhang Xu , Ruiyi Zhou , Tao E. Li , Sharon Hammes-Schiffer , Yosuke Kanai

Proton transfer is central to many processes of chemical interest. The simulation of proton transfer dynamics requires the inclusion of nuclear quantum effects, such as zero-point energy, nuclear delocalization, and tunneling. Herein, we…

Chemical Physics · Physics 2026-03-19 Joseph A. Dickinson , Mathew Chow , Eno Paenurk , Sharon Hammes-Schiffer

The coupled quantum dynamics of electrons and protons is ubiquitous in many dynamical processes involving light-matter interaction, such as solar energy conversion in chemical systems and photosynthesis. A first-principles description of…

Chemical Physics · Physics 2023-11-07 Jianhang Xu , Ruiyi Zhou , Tao E. Li , Volker Blum , Sharon Hammes-Schiffer , Yosuke Kanai

In Born-Oppenheimer molecular dynamics (BOMD) simulations based on density functional theory (DFT), the potential energy and the interatomic forces are calculated from an electronic ground state density that is determined by an iterative…

Chemical Physics · Physics 2023-05-03 Anders M. N. Niklasson , Christian F. A. Negre

We introduce a method to carry out zero-temperature calculations within density functional theory (DFT) but without relying on the Born-Oppenheimer (BO) approximation for the ionic motion. Our approach is based on the finite-temperature…

Materials Science · Physics 2018-11-21 Grigory Kolesov , Efthimios Kaxiras , Efstratios Manousakis

An attractive way to model nuclear quantum effects is to describe select nuclei quantum mechanically at the same level as the electrons. This non-Born-Oppenheimer (non-BO) method is known by many names including the nuclear-electronic…

Chemical Physics · Physics 2026-04-20 Luukas Nikkanen , Susi Lehtola

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

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

An atomic-orbital basis set framework is presented for carrying out velocity- gauge real-time time-dependent density functional theory (TDDFT) simulations in periodic systems employing range-separated hybrid functionals. Linear optical…

Materials Science · Physics 2018-10-02 C. D. Pemmaraju

Extended Lagrangian Born-Oppenheimer molecular dynamics (XL-BOMD) [Phys. Rev. Lett. vol. 100, 123004 (2008)] is combined with Kohn-Sham density functional theory (DFT) using a DFT+U correction based on the Hubbard model. This combined…

Phase-space electronic structure theory offers up a new and powerful approach for tackling problems with coupled nuclear-electronic dynamics in a fashion that goes beyond Born-Oppenheimer (BO) theory. Whereas BO theory stipulates that we…

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
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