相关论文: On the Breakdown of the Ehrenfest Method for Molec…
Mixed quantum-classical methods, such as surface hopping and Ehrenfest dynamics, have proven useful for describing molecular processes involving multiple electronic states. These methods require propagating many independent trajectories,…
Density functional theory with linear combination of atomic orbitals (LCAO) basis sets is useful for studying large atomic systems, especially when it comes to computationally highly demanding time-dependent dynamics. We have implemented…
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…
Mixed quantum-classical mechanics descriptions are critical to modeling coupled electron-nuclear dynamics, i.e. non-adiabatic molecular dynamics, relevant to photochemical and photophysical processes. We argue that, for polyatomic…
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…
Electronic friction and Langevin dynamics is a popular mixed quantum-classical method for simulating the nonadiabatic dynamics of molecules interacting with metal surfaces, as it can be computationally more efficient than fully quantum…
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…
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…
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…
A theory of electronic friction is developed using the exact factorization of the electron-nuclear wavefunction. No assumption is made regarding the electronic bath, which can be made of independent or interacting electrons, and the nuclei…
Molecular adsorbates on metal surfaces exchange energy with substrate phonons and low-lying electron-hole pair excitations. In the limit of weak coupling, electron-hole pair excitations can be seen as exerting frictional forces on…
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…
Electronic friction-Langevin dynamics (EF-LD) provides an efficient framework for capturing nonadiabatic effects at solid surfaces, with particular relevance to electrochemistry and molecular electronics. In this work, we investigate…
A new scheme is proposed for modeling molecular nonadiabatic dynamics near metal surfaces. The charge-transfer character of such dynamics is exploited to construct an efficient reduced representation for the electronic structure. In this…
Being a numerically exact method for the simulation of dynamics in open quantum systems, the hierarchical equations of motion (HEOM) still suffers from the curse of dimensionality. In this study, we propose a novel MCE-HEOM method, which…
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…
Nonadiabatic effects that arise from the concerted motion of electrons and atoms at comparable energy and time scales are omnipresent in thermal and light-driven chemistry at metal surfaces. Excited (hot) electrons can measurably affect…
Simulating electron-ion dynamics using time-dependent density functional theory within an Ehrenfest dynamics scheme can be done in two ways that are in principle exact and identical: propagating time-dependent electronic Kohn-Sham equations…
We derive an explicit form for the electronic friction as felt by a molecule near a metal surface for the general case that molecule-metal couplings depend on nuclear coordinates. Our work generalizes a previous study by von Oppen et al…
In this work we propose an extension to the analytical one-dimensional model proposed by E. Gnecco (Phys. Rev. Lett. 84:1172) to describe friction. Our model includes normal forces and the dependence with the angular direction of movement…