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Experiments indicate that collective coupling of molecular ensembles to confined optical modes can modify excited-state dynamics and photochemical reactivity. To describe such cavity-induced effects at atomic resolution, semi-classical…

Chemical Physics · Physics 2026-03-06 Arun Kumar Kanakati , Oriol Vendrell , Gerrit Groenhof

We develop a density matrix formalism to describe coupled electron-nuclear dynamics. To this end we introduce an effective Hamiltonian formalism that describes electronic transitions and small (quantum) nuclear fluctuations along a…

Chemical Physics · Physics 2020-09-07 Eugene Stolyarov , Alexander White , Dmitry Mozyrsky

Using a combination of high-level ab initio electronic structure methods with efficient on-the-fly semiclassical evaluation of nuclear dynamics, we performed a massive scan of small polyatomic molecules searching for a long lasting…

Chemical Physics · Physics 2024-09-26 Alan Scheidegger , Jiří Vaníček , Nikolay V. Golubev

Non-adiabatic dynamics simulations have become a standard approach to explore photochemical reactions. Such simulations require underlying potential energy surfaces and couplings between them, calculated at a chosen level of theory, yet…

Chemical Physics · Physics 2024-05-28 Thomas V. Papineau , Denis Jacquemin , Morgane Vacher

Nonadiabatic dynamical processes are one of the most important quantum mechanical phenomena in chemical, materials, biological, and environmental molecular systems, where the coupling between different electronic states is either inherent…

Chemical Physics · Physics 2022-05-24 Jian Liu , Xin He , Baihua Wu

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

We implement a rare-event sampling scheme for quantifying the rate of thermally-activated nonadiabatic transitions in the condensed phase. Our QM/MM methodology uses the recently developed INAQS package to interface between an elementary…

Chemical Physics · Physics 2023-03-23 Alec J. Coffman , Zuxin Jin , Junhan Chen , Joseph E. Subotnik , D. Vale Cofer-Shabica

An accurate description of nonadiabatic dynamics of molecular species on metallic surfaces poses a serious computational challenge associated with a multitude of closely-spaced electronic states. We propose a mixed quantum-classical scheme…

Chemical Physics · Physics 2017-01-10 Ilya G. Ryabinkin , Artur F. Izmaylov

We show how the dynamically nonlocal formulation of classical nuclear motion in the presence of quantal electronic transitions presented many years ago by Pechukas can be localized in time using time dependent perturbation theory to give an…

chem-ph · Physics 2009-10-22 D. F. Coker , L. Xiao

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

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

The quantum-classical Liouville equation offers a rigorous approach to nonadiabatic quantum dynamics based on surface hopping type trajectories. However, in practice the applicability of this approach has been limited to short times owing…

Chemical Physics · Physics 2015-06-16 Aaron Kelly , Thomas E. Markland

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 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

We investigate a simple and robust scheme for choosing the phases of adiabatic electronic states smoothly (as a function of geometry) so as to maximize the performance of ab initio non-adiabatic dynamics methods. Our approach is based upon…

Chemical Physics · Physics 2019-09-26 Zeyu Zhou , Zuxin Jin , Tian Qiu , Andrew M. Rappe , Joseph Eli Subotnik

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

Non-adiabatic dynamics at molecule-metal interfaces govern diverse and technologically important phenomena, from heterogeneous catalysis to dye-sensitized solar energy conversion and charge transport across molecular junctions. Realistic…

Quantum Physics · Physics 2026-02-27 Robert A. Lang , Paarth Jain , Juan Miguel Arrazola , Danial Motlagh

Irradiation of a molecular system by an intense laser field can trigger dynamics of both electronic and nuclear subsystems. The lighter electrons usually move on much faster, attosecond time scale but the slow nuclear rearrangement damps…

Chemical Physics · Physics 2020-08-26 Nikolay V. Golubev , Tomislav Begušić , Jiří Vaníček

In Thouless pump, the charge transport in a one-dimensional insulator over an adiabatic cycle is topologically quantized. For nonequilibrium initial states, however, interband coherence will induce a previously unknown contribution to…

Mesoscale and Nanoscale Physics · Physics 2020-05-13 Gudapati Naresh Raghava , Longwen Zhou , Jiangbin Gong

A wide range of ultrafast phenomena in various atomic, molecular and condense matter systems is governed by electron dynamics. Therefore, the ability to image electronic motion in real space and real time would provide a deeper…

Atomic Physics · Physics 2018-02-27 Daria Popova-Gorelova