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Exposing a molecule to intense light pulses may bring this molecule to a nonstationary quantum state, thus launching correlated dynamics of electronic and nuclear subsystems. Although much had been achieved in the understanding of…

Chemical Physics · Physics 2024-04-11 Nikolay V. Golubev , Jiří Vaníček

The recent improvement in experimental capabilities for interrogating and controlling molecular systems with ultrafast coherent light sources calls for the development of theoretical approaches that can accurately and efficiently treat…

Chemical Physics · Physics 2024-08-20 Jonathan R. Mannouch , Aaron Kelly

The optical response of an electronic two-level system (TLS) coupled to an incident continuous wave (cw) electromagnetic (EM) field is simulated explicitly in one dimension by the following five approaches: (i) the coupled Maxwell-Bloch…

Optics · Physics 2019-03-19 Tao E. Li , Hsing-Ta Chen , Joseph E. Subotnik

The dynamics of an electronic system interacting with an electromagnetic field is investigated within mixed quantum-classical theory. Beyond the classical path approximation (where we ignore all feedback from the electronic system on the…

Chemical Physics · Physics 2019-02-11 Hsing-Ta Chen , Tao E. Li , Maxim Sukharev , Abraham Nitzan , Joseph E. Subotnik

A novel mixed quantum-classical approach to simulating nonadiabatic dynamics of molecules at metal surfaces is presented. The method combines the numerically exact hierarchical equations of motion approach for the quantum electronic degrees…

Mesoscale and Nanoscale Physics · Physics 2024-05-06 Samuel L. Rudge , Christoph Kaspar , Robin L. Grether , Steffen Wolf , Gerhard Stock , Michael Thoss

Interest in vibrational polaritonic chemistry, where ground-state chemical kinetics are modified via confined optical modes in a cavity, has surged in recent years. Although models have been developed to understand cavity-modified…

Quantum Physics · Physics 2025-02-10 Muhammad R. Hasyim , Arkajit Mandal , David R. Reichman

Adequate simulation of non-adiabatic dynamics through conical intersection requires account for a non-trivial geometric phase (GP) emerging in electronic and nuclear wave-functions in the adiabatic representation. Popular mixed…

Chemical Physics · Physics 2015-07-20 Rami Gherib , Ilya G. Ryabinkin , Artur F. Izmaylov

We describe vacuum fluctuations and photon-field correlations in interacting quantum mechanical light-matter systems, by generalizing the application of mixed quantum-classical dynamics techniques. We employ the multi-trajectory…

Quantum Physics · Physics 2019-06-26 Norah M. Hoffmann , Christian Schäfer , Angel Rubio , Aaron Kelly , Heiko Appel

While the treatment of chemically relevant systems containing hundreds or even thousands of electrons remains beyond the reach of quantum devices, the development of quantum-classical hybrid algorithms to resolve electronic correlation…

Due to the exponential growth of the state space of coupled quantum systems it is not possible, in general, to numerically store the state of a very large number of quantum systems within a classical computer. We demonstrate a method for…

Quantum Physics · Physics 2017-02-07 J. J. Bowen , V. M. Dwyer , I. W. Phillips , M. J. Everitt

Semiclassical electrodynamics is an appealing approach for studying light-matter interactions, especially for realistic molecular systems. However, there is no unique semiclassical scheme. On the one hand, intermolecular interactions can be…

Chemical Physics · Physics 2019-12-16 Tao E. Li , Hsing-Ta Chen , Abraham Nitzan , Joseph E. Subotnik

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…

The exact factorization approach has led to the development of new mixed quantum-classical methods for simulating coupled electron-ion dynamics. We compare their performance for dynamics when more than two electronic states are occupied at…

The violation of detailed balance poses a serious problem for the majority of current quasiclassical methods for simulating nonadiabatic dynamics. In order to analyze the severity of the problem, we predict the long-time limits of the…

Quantum Physics · Physics 2023-11-20 Graziano Amati , Jonathan R. Mannouch , Jeremy O. Richardson

The mapping approach addresses the mismatch between the continuous nuclear phase space and discrete electronic states by creating an extended, fully continuous phase space using a set of harmonic oscillators to encode the populations and…

Chemical Physics · Physics 2019-09-30 Maximilian A. C. Saller , Aaron Kelly , Jeremy O. Richardson

When the interaction between a molecular system and confined light modes in an optical or plasmonic cavity is strong enough to overcome the dissipative process, hybrid light-matter states (polaritons) emerge as the fundamental excitations…

Chemical Physics · Physics 2024-10-23 Xinyang Li , Sergei Tretiak , Yu Zhang

We introduce a novel methodology for simulating the excited-state dynamics of extensive molecular aggregates in the framework of the long-range corrected time-dependent density-functional tight-binding fragment molecular orbital method…

Chemical Physics · Physics 2024-04-23 Richard Einsele , Roland Mitrić

We introduce a novel computational framework for excited-states molecular quantum dynamics simulations driven by quantum computing-based electronic-structure calculations. This framework leverages the fewest-switches surface-hopping method…

Quantum Physics · Physics 2024-02-26 Anthony Gandon , Alberto Baiardi , Pauline Ollitrault , Ivano Tavernelli

Understanding the electron dynamics and transport in metallic and semiconductor nanostructures -- such as metallic nanoparticles, thin films, quantum wells and quantum dots -- represents a considerable challenge for today's condensed matter…

Strongly Correlated Electrons · Physics 2008-10-20 G. Manfredi , P. -A. Hervieux , Y. Yin , N. Crouseilles

We present a nonadiabatic classical-trajectory approach that offers the best of both worlds between fewest-switches surface hopping (FSSH) and quasiclassical mapping dynamics. This mapping approach to surface hopping (MASH) propagates the…

Chemical Physics · Physics 2023-03-29 Jonathan R. Mannouch , Jeremy O. Richardson