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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…

We propose to measure nonadiabaticity of molecular quantum dynamics rigorously with the quantum fidelity between the Born-Oppenheimer and fully nonadiabatic dynamics. It is shown that this measure of nonadiabaticity applies in situations…

Chemical Physics · Physics 2012-06-28 Tomas Zimmermann , Jiri Vanicek

We propose a novel method to describe realistically ionization processes with absorbing boundary conditions in basis expansion within the formalism of the so-called Non-Adiabatic Quantum Molecular Dynamics. This theory couples…

Quantum Physics · Physics 2015-06-26 Mathias Uhlmann , Thomas Kunert , Ruediger Schmidt

Every physical regime is some sort of approximation of reality. One lesser-known realm that is the semiquantal regime, which may be used to describe systems with both classical and quantum subcomponents. In the present review, we discuss…

Chaotic Dynamics · Physics 2009-11-07 Mason A. Porter

In this paper, we present a variational treatment of the linear dependence for a non-orthogonal time-dependent basis set in solving the Schr\"odinger equation. The method is based on: i) the definition of a linearly independent working…

Quantum Physics · Physics 2022-10-12 Loïc Joubert-Doriol

We propose a trajectory-based method for simulating nonadiabatic dynamics in molecular systems with two coupled electronic states. Employing a quantum-mechanically exact mapping of the two-level problem to a spin-1/2 coherent state, we…

Chemical Physics · Physics 2020-03-03 Johan E. Runeson , Jeremy O. Richardson

We propose an approximate method for evaluating the importance of non-Born-Oppenheimer effects on the quantum dynamics of nuclei. The method uses a generalization of the dephasing representation (DR) of quantum fidelity to several diabatic…

Chemical Physics · Physics 2013-01-15 Tomas Zimmermann , Jiri Vanicek

We propose an excited-state molecular dynamics simulation method based on variational quantum algorithms at a computational cost comparable to that of ground-state simulations. We utilize the feature that excited states can be obtained as…

Chemical Physics · Physics 2023-03-02 Hirotoshi Hirai

We derive an exact quantum propagator for nonadiabatic dynamics in multi-state systems using the mapping variable representation, where classical-like Cartesian variables are used to represent both continuous nuclear degrees of freedom and…

Chemical Physics · Physics 2017-07-25 Timothy J. H. Hele , Nandini Ananth

This article discusses applications of Bayesian machine learning for quantum molecular dynamics. One particular formulation of quantum dynamics advocated here is in the form of a machine learning simulator of the Schr\"{o}dinger equation.…

Chemical Physics · Physics 2019-07-24 R. V. Krems

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 how non-adiabatic terms affect quantum dynamics is fundamental to improving various protocols for quantum technologies. We present a novel approach to computing the Adiabatic Gauge Potential (AGP), which gives information on…

Quantum Physics · Physics 2025-01-15 Ewen D C Lawrence , Sebastian F J Schmid , Ieva Čepaitė , Peter Kirton , Callum W Duncan

Nonadiabatic molecular dynamics is an effective method for modeling nonradiative decay in electronically excited molecules. Its accuracy depends strongly on the quality of the potential energy surfaces, and its affordability for long…

Chemical Physics · Physics 2024-10-11 Matthew R. Hennefarth , Donald G. Truhlar , Laura Gagliardi

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

A first principles quantum formalism to describe the non-adiabatic dynamics of electrons and nuclei based on a second quantization representation (SQR) of the electronic motion combined with the usual representation of the nuclear…

Chemical Physics · Physics 2020-11-06 Sudip Sasmal , Oriol Vendrell

Adiabatic Quantum Computing relies on the quantum adiabatic theorem, which states that a quantum system evolves along its ground state with time if the governing Hamiltonian varies infinitely slowly. However, practical limitations force…

Ab initio methods for electronic structure of molecules have reached a satisfactory accuracy for calculation of static properties, but remain too expensive for quantum dynamical calculations. We propose an efficient semiclassical method for…

Chemical Physics · Physics 2015-05-13 Baiqing Li , Cesare Mollica , Jiri Vanicek

This paper provides the first ab-initio on-the-fly example of using the Quasi-Diabatic (QD) scheme for non-adiabatic simulations with diabatic dynamics approaches. The QD scheme provides a seamless interface between diabatic quantum…

Computational Physics · Physics 2019-08-15 Wanghuai Zhou , Arkajit Mandal , Pengfei Huo

A Gaussian operator basis provides a means to formulate phase-space simulations of the real- and imaginary-time evolution of quantum systems. Such simulations are guaranteed to be exact while the underlying distribution remains…

Computational Physics · Physics 2012-04-04 M. Ogren , K. V. Kheruntsyan , J. F. Corney

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