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Density functional theory with linear combination of atomic orbitals (LCAO) basis sets is useful for studying large atomic systems, especially when it comes to computationally highly demanding time-dependent dynamics. We have implemented…

Materials Science · Physics 2025-05-02 Vladimír Zobač , Mikael Kuisma , Ask Hjorth Larsen , Tuomas Rossi , Toma Susi

Ehrenfest Dynamics combined with real-time time-dependent density functional theory has proven to be a reliable tool to study non-adiabatic molecular dynamics with a reasonable computational cost. Among other possibilities, it allows for…

Materials Science · Physics 2023-01-05 Ronaldo Rodrigues Pela , Claudia Draxl

Mixed quantum-classical mechanics descriptions are critical to modeling coupled electron-nuclear dynamics, i.e. non-adiabatic molecular dynamics, relevant to photochemical and photophysical processes. We argue that, for polyatomic…

Chemical Physics · Physics 2018-08-21 Roman Baskov , Alexander White , Dmitry Mozyrsky

Ehrenfest dynamics is a useful approximation for ab initio mixed quantum-classical molecular dynamics that can treat electronically nonadiabatic effects. Although a severe approximation to the exact solution of the molecular time-dependent…

Chemical Physics · Physics 2021-09-24 Seonghoon Choi , Jiří Vaníček

Mixed quantum-classical methods, such as surface hopping and Ehrenfest dynamics, have proven useful for describing molecular processes involving multiple electronic states. These methods require propagating many independent trajectories,…

Chemical Physics · Physics 2025-08-15 Alan Scheidegger , Jiří J. L. Vaníček

The exact nuclear time-dependent potential energy surface arises from the exact decomposition of electronic and nuclear motion, recently presented in [A. Abedi, N. T. Maitra, and E. K. U. Gross, Phys. Rev. Lett. 105, 123002 (2010)]. Such…

Chemical Physics · Physics 2015-06-16 Federica Agostini , Ali Abedi , Yasumitsu Suzuki , E. K. U. Gross

Accurate simulation of the non-adiabatic dynamics of molecules in excited electronic states is key to understanding molecular photo-physical processes. Here we present a novel method, based on a semiclassical approximation, that is as…

Chemical Physics · Physics 2016-05-24 Alexander White , Sergei Tretiak , Dmitry Mozyrsky

We present in detail the recently derived ab-initio molecular dynamics (AIMD) formalism [Phys. Rev. Lett. 101 096403 (2008)], which due to its numerical properties, is ideal for simulating the dynamics of systems containing thousands of…

We discuss the evolution of purity in mixed quantum/classical approaches to electronic nonadiabatic dynamics in the context of the Ehrenfest model. As it is impossible to exactly determine initial conditions for a realistic system, we…

Chemical Physics · Physics 2012-09-07 J. L. Alonso , J. Clemente-Gallardo , J. C. Cuchí , P. Echenique , F. Falceto

Incorporating nuclear quantum effects into nonadiabatic dynamics remains a significant challenge. Herein we introduce new nonadiabatic dynamics approaches based on the recently developed constrained nuclear-electronic orbital (CNEO) theory.…

Chemical Physics · Physics 2025-04-15 Zhe Liu , Zehua Chen , Yang Yang

Application of the time-dependent variational principle to a linear combination of frozen-width Gaussians describing the nuclear wavefunction provides a formalism where the total energy is conserved. The computational downside of this…

Chemical Physics · Physics 2022-06-15 Mina Asaad , Loïc Joubert-Doriol , Artur F. Izmaylov

A new "on the fly" method to perform Born-Oppenheimer ab initio molecular dynamics (AIMD) is presented. Inspired by Ehrenfest dynamics in time-dependent density functional theory, the electronic orbitals are evolved by a Schroedinger-like…

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

We benchmark a set of quantum-chemistry methods, including multitrajectory Ehrenfest, fewest-switches surface-hopping, and multiconfigurational-Ehrenfest dynamics, against exact quantum-many-body techniques by studying real-time dynamics in…

In this work, we present a computationally efficient methodology that utilizes a local real-space formulation of the projector augmented wave (PAW) method discretized with a finite-element (FE) basis to enable accurate and large-scale…

Computational Physics · Physics 2025-01-03 Kartick Ramakrishnan , Sambit Das , Phani Motamarri

The Ehrenfest dynamics, representing a quantum-classical mean-field type coupling, is a widely used approximation in quantum molecular dynamics. In this paper, we propose a time-splitting method for an Ehrenfest dynamics, in the form of a…

Numerical Analysis · Mathematics 2022-10-19 Di Fang , Shi Jin , Christof Sparber

The projector augmented wave (PAW) method of Bl\"ochl linearly maps smooth pseudo wavefunctions to the highly oscillatory all-electron DFT orbitals. Compared to norm-conserving pseudopotentials (NCPP), PAW has the advantage of lower kinetic…

Chemical Physics · Physics 2023-12-25 Minh Nguyen , Tim Duong , Daniel Neuhauser

One key challenge in the study of nonadiabatic dynamics in open quantum systems is to balance computational efficiency and accuracy. Although Ehrenfest dynamics (ED) is computationally efficient and well-suited for large complex systems, ED…

Quantum Physics · Physics 2024-12-02 Jingqi Chen , Joonho Lee , Wenjie Dou

In the Projector Augmented Wave (PAW) method, a local potential, basis functions, and projector functions form an All-Electron (AE) basis for valence wave functions in the application of Density Functional Theory (DFT). The construction of…

Materials Science · Physics 2010-08-05 R. J. Snow , A. F. Wright , C. Y. Fong

Ehrenfest and Car-Parrinello molecular dynamics are computational alternatives to approximate Born-Oppenheimer molecular dynamics without solving the electron eigenvalue problem at each time-step. A non-trivial issue is to choose the…

Chemical Physics · Physics 2014-09-18 Ashraful Kadir , Mattias Sandberg , Anders Szepessy
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