Related papers: An Improved Ehrenfest Approach to Model Correlated…
We describe a path-integral approach for including nuclear quantum effects in non-adiabatic chemical dynamics simulations. For a general physical system with multiple electronic energy levels, a corresponding isomorphic Hamiltonian is…
The Ehrenfest dynamics, representing a quantum-classical mean-field type coupling, is a widely used approximation in quantum molecular dynamics. In this paper, we propose a time-splitting method for an Ehrenfest dynamics, in the form of a…
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…
A much-needed solution for the efficient modeling of strong coupling between matter and optical cavity modes is offered by mean-field mixed quantum--classical dynamics, where a classical cavity field interacts self-consistently with quantum…
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…
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…
Nonadiabatic transition dynamics lies at the core of many electron/hole transfer, photoactivated, and vacuum field-coupled processes. About a century after Ehrenfest proposed "Phasenraum" and the Ehrenfest theorem, we report a conceptually…
Computational chemistry at the atomic level has largely branched into two major fields, one based on quantum mechanics and the other on molecular mechanics using classical force fields. Because of high computational costs, quantum…
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…
We develop a linear vibronic coupling (LVC) model for polyenes described by the extended Hubbard-Peierls Hamiltonian. This model is applied to trans-hexatriene to benchmark quantum-classical dynamics methods against fully quantum…
A general theoretical framework is derived for the recently developed multi-state trajectory (MST) approach from the time dependent Schr\"odinger equation, resulting in equations of motion for coupled nuclear-electronic dynamics equivalent…
We propose mixed quantum-classical equations of motion that unify electronic coherence and phase evolution simultaneously within the exact factorization framework. Our derivation shows that incorporating the second-order electron-nuclear…
Molecules in molecular junctions are subject to current-induced forces that can break chemical bonds, induce reactions, destabilize molecular geometry, and halt the operation of the junction. Theories behind current-driven molecular…
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…
The quantum dynamics of electron-nuclear systems is analyzed from the perspective of the exact factorization of the wavefunction, with the aim of defining gauge invariant equations of motion for both the nuclei and the electrons. For pure…
Known force terms arising in the Ehrenfest dynamics of quantum electrons and classical nuclei, due to a moving basis set for the former, can be understood in terms of the curvature of the manifold hosting the quantum states of the…
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…
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 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…
We developed a general theoretical approach and a user-ready computer code that permit to study the dynamics of collisional energy transfer and ro-vibrational energy exchange in complex molecule-molecule collisions. The method is a mixture…