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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

Nonadiabatic coupling between electrons and molecular motion at metal surfaces leads to energy dissipation and dynamical steering effects during chemical surface dynamics. We present a theoretical approach to the scattering of molecules…

Energy loss in collisions of charged projectiles with many-electron systems can be dealt with in time-dependent density functional theory by invoking Ehrenfest's theorem for the time evolution of expectation values of observables. We derive…

Atomic Physics · Physics 2021-09-15 Hans Jürgen Lüdde , Marko Horbatsch , Tom Kirchner

We develop a unified theory for the nonadiabatic wave-packet dynamics of Bloch electrons subject to slowly varying spatial and temporal perturbations. Extending the conventional wave-packet ansatz to include interband contributions, we…

Materials Science · Physics 2026-04-13 Yafei Ren , M. E. Sanchez Barrero

We examine the challenge of performing accurate electronic structure calculations at high pressures by comparing the results of all-electron full potential linearized augmented-plane-wave calculations with those of the projector augmented…

Computational Physics · Physics 2018-01-11 Kanchan Sarkar , Mehmet Topsakal , N. A. W. Holzwarth , Renata M. Wentzcovitch

A new methodology of simulating nonadiabatic dynamics using frozen-width Gaussian wavepackets within the moving crude adiabatic representation with the on-the-fly evaluation of electronic structure is presented. The main feature of the new…

Chemical Physics · Physics 2018-04-04 Loïc Joubert-Doriol , Artur F. Izmaylov

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…

Linear and nonlinear electronic spectra provide an important tool to probe the absorption and transfer of electronic energy. Here we introduce a pure state Ehrenfest approach to obtain accurate linear and nonlinear spectra that is…

Chemical Physics · Physics 2022-12-15 Austin O. Atsango , Andrés Montoya-Castillo , Thomas E. Markland

Two-dimensional electronic spectroscopy (2DES) provides a detailed picture of electronically nonadiabatic dynamics that can be interpreted with the aid of simulations. Here, we develop and contrast trajectory-based nonadiabatic dynamics…

Real-time simulations of laser-driven electron dynamics contain information about molecular optical properties through all orders in response theory. These properties can be extracted by assuming convergence of the power series expansion of…

The computational investigation of photochemical processes often entails the calculation of excited state geometries, energies, and energy gradients. The nuclear-electronic orbital (NEO) approach treats specified nuclei, typically protons,…

A non-adiabatic nuclear wavepacket dynamics simulation of the H$_2$O$^+$ de-excitation process is performed based on electronic structure calculations using the variational quantum eigensolver. The adiabatic potential energy surfaces and…

Quantum Physics · Physics 2022-03-02 Hirotoshi Hirai , Sho Koh

In Kohn-Sham electronic structure computations, wave functions have singularities at nuclear positions. Because of these singularities, plane-wave expansions give a poor approximation of the eigenfunctions. In conjunction with the use of…

Numerical Analysis · Mathematics 2023-01-02 Xavier Blanc , Eric Cancès , Mi-Song Dupuy

Nonadiabatic molecular dynamics occur in a wide range of chemical reactions and femtochemistry experiments involving electronically excited states. These dynamics are hard to treat numerically as the system's complexity increases and it is…

Chemical Physics · Physics 2021-07-28 Haifeng Lang , Oriol Vendrell , Philipp Hauke

The thawed Gaussian Ehrenfest dynamics is a single-trajectory method that partially includes both nuclear quantum and electronically nonadiabatic effects by combining the thawed Gaussian wavepacket dynamics with Ehrenfest dynamics. First,…

Chemical Physics · Physics 2025-04-09 Alan Scheidegger , Jiří J. L. Vaníček

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 consider an Ehrenfest approximation for a particle in a double-well potential in the presence of an external environment schematized as a finite resource heat bath. This allows us to explore how the limitations in the applicability of…

Quantum Physics · Physics 2015-10-09 Stephen Choi , Roberto Onofrio , Bala Sundaram

Recently introduced methods which result in shortcuts to adiabaticity, particularly in the context of frictionless cooling, are rederived and discussed in the framework of an approach based on Ehrenfest dynamics. This construction provides…

Quantum Gases · Physics 2015-06-17 S. Choi , R. Onofrio , B. Sundaram

Nuclear quantum effects and non-Born--Oppenheimer effects play a vital role in many chemical and biological processes, motivating the incorporation of such effects into dynamical simulations. In real-time nuclear--electronic orbital…

Chemical Physics · Physics 2026-05-27 Nicholas J. Boyer , Sharon Hammes-Schiffer

We consider a charged particle driven by a time-dependent flux threading a quantum ring. The dynamics of the charged particle is investigated using classical treatment, Fourier expansion technique, time-evolution method, and…

Mesoscale and Nanoscale Physics · Physics 2008-07-29 Pi-Gang Luan , Chi-Shung Tang