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Chemical relaxation phenomena, including photochemistry and electron transfer processes, form a vigorous area of research in which nonadiabatic dynamics plays a fundamental role. Here, we show that for nonadiabatic dynamics with two…

Chemical Physics · Physics 2022-07-20 Yanze Wu , Xuezhi Bian , Jonathan Rawlinson , Robert G. Littlejohn , Joseph E. Subotnik

Linear-response quantum electrodynamical density functional theory (QEDFT) enables the description of molecular spectra under strong coupling to quantized photonic modes, such as those in optical cavities. Recently, this approach was…

Chemical Physics · Physics 2025-07-11 Lukas Konecny , Valeriia P. Kosheleva , Michael Ruggenthaler , Michal Repisky , Angel Rubio

A generalized formalism of the so-called non-adiabatic quantum molecular dynamics is presented, which applies for atomic many-body systems in external laser fields. The theory treats the nuclear dynamics and electronic transitions…

Atomic Physics · Physics 2007-05-23 Thomas Kunert , Ruediger Schmidt

We present an efficient \textit{ab initio} algorithm for quantum dynamics simulations of interacting systems that is based on the conditional decomposition of the many-body wavefunction [Phys. Rev. Lett. 113, 083003 (2014)]. Starting with…

Mesoscale and Nanoscale Physics · Physics 2019-02-27 Guillermo Albareda , Aaron Kelly , Angel Rubio

We build on the concept of eigenvector continuation to develop an efficient multi-state method for the rigorous and smooth interpolation of a small training set of many-body wavefunctions through chemical space at mean-field cost. The…

Chemical Physics · Physics 2024-05-02 Kemal Atalar , Yannic Rath , Rachel Crespo-Otero , George H. Booth

The primary computational challenge when simulating nonadiabatic ab initio molecular dynamics is the unfavorable compute costs of electronic structure calculations with molecular size. Simple electronic structure theories, like…

Chemical Physics · Physics 2023-06-28 Justin J. Talbot , Martin Head-Gordon , Stephen J. Cotton

Complete active space self-consistent field (CASSCF) computations can be realized at polynomial cost via the variational optimization of the active-space two-electron reduced-density matrix (2-RDM). Like conventional approaches to CASSCF,…

Chemical Physics · Physics 2018-12-10 Mohammad Mostafanejad , A. Eugene DePrince

We propose a nonadiabatic time-dependent spin-density functional theory (TDSDFT) approach for studying the single-electron excited states and the ultrafast response of systems with strong electron correlations. The correlations are…

Strongly Correlated Electrons · Physics 2013-11-27 Volodymyr Turkowski , Talat S. Rahman

Nonadiabatic dynamics methods are an essential tool for investigating photochemical processes. In the context of employing first principles electronic structure techniques, such simulations can be carried out in a practical manner using…

Chemical Physics · Physics 2024-05-08 Jonathan R. Mannouch , Aaron Kelly

Accurate description of nonadiabatic dynamics of molecules at metal surfaces involving electron transfer has been a longstanding challenge for theory. Here, we tackle this problem by first constructing high-dimensional neural network…

Materials Science · Physics 2024-01-05 Gang Meng , James Gardner , Wenjie Dou , Reinhard J. Maurer , Bin Jiang

The superadiabatic dynamical density functional theory (superadiabatic-DDFT) is a promising new method for the study of colloidal systems out-of-equilibrium. Within this approach the viscous forces arising from interparticle interactions…

Soft Condensed Matter · Physics 2024-06-10 S. M. Tschopp , J. M. Brader

On-the-fly quantum nonadiabatic dynamics for large systems greatly benefits from the adiabatic representation readily available from the electronic structure programs. However, frequently occurring in this representation conical…

Most applications of time-dependent density-functional theory (TDDFT) use the adiabatic local-density approximation (ALDA) for the dynamical exchange-correlation potential Vxc(r,t). An exact (i.e., nonadiabatic) extension of the…

Mesoscale and Nanoscale Physics · Physics 2015-06-25 C. A. Ullrich

Excited-state molecular dynamics (ESMD) simulations near conical intersections (CIs) pose significant challenges when using machine learning potentials (MLPs). Although MLPs have gained recognition for their integration into mixed…

Chemical Physics · Physics 2025-01-17 Sung Wook Moon , Soohaeng Yoo Willow , Tae Hyeon Park , Seung Kyu Min , Chang Woo Myung

A software package, called DFTBaby, is published, which provides the electronic structure needed for running non-adiabatic molecular dynamics simulations at the level of charge-consistent tight-binding DFT. A long-range correction is…

Chemical Physics · Physics 2017-10-25 Alexander Humeniuk , Roland Mitric

Superadiabatic dynamical density functional theory (superadiabatic-DDFT), a first-principles approach based on the inhomogeneous two-body correlation functions, is employed to investigate the response of interacting Brownian particles to…

Soft Condensed Matter · Physics 2023-06-23 S. M. Tschopp , H. D. Vuijk , J. M. Brader

The combined quantum electron-nuclear dynamics is often associated with the Born-Huang expansion of the molecular wave function and the appearance of nonadiabatic effects as a perturbation. On the other hand, native multicomponent…

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

Nonadiabatic molecular dynamics is a key technique for investigating a broad range of photochemical and photophysical processes. Among the established approaches, surface hopping schemes are widely used and can be easily integrated with…

Chemical Physics · Physics 2025-12-23 Jakub Martinka , Mikołaj Martyka , Biman Medhi , Jiří Pittner , Pavlo O. Dral

Ideal density-functional approximations (DFAs) should account for dynamic, static, and nondynamic correlation. While common DFAs struggle with the latter two, the Ziegler-Rauk-Baerends-Daul multiplet sum method (MSM) provides a pragmatic…

Chemical Physics · Physics 2026-05-29 Mark E Casida , Abraham Ponra , Gadzikano Munyuki , Bharathi Natarajan