相关论文: Electronic non-adiabatic states
This report presents a new approach for treating the coupling of electrons and nuclei in quantum mechanical calculations for molecules and condensed matter. It includes the standard "Born-Oppenheimer approximation" as a special case but…
We propose a procedure to analyze the relation between the exact factorization of the electron-nuclear wave function and the Born-Oppenheimer approximation. We define the adiabatic limit as the limit of infinite nuclear mass. To this end,…
We perform model calculations for a stretched LiF molecule, demonstrating that nonadiabatic charge transfer effects can be accurately and seamlessly described within a density functional framework. In alkali halides like LiF, there is an…
The thorough treatment of electron-lattice interactions from first principles is one of the main goals in condensed matter physics. While the commonly applied adiabatic Born-Oppenheimer approximation is sufficient for describing many…
The Born-Oppenheimer approximation leads to the counterintuitive result of a vanishing electronic flux density upon vibrational dynamics in the electronic ground state. To circumvent this long known issue, we propose using pairwise…
The interaction between electronic and vibrational degrees of freedom is an important mechanism in nonequilibrium charge transport through molecular nanojunctions. While adiabatic polaron-type coupling has been studied in great detail, new…
The molecular Schr\"odinger equation is rewritten in terms of non-unitary equations of motion for the nuclei (or electrons) that depend parametrically on the configuration of an ensemble of generally defined electronic (or nuclear)…
We present explicit form of non-adiabatic coupling (NAC) elements of nuclear Schroedinger equation (SE) for a coupled tri-state electronic manifold in terms of mixing angles of real electronic basis functions. If the adiabatic-diabatic…
In the context of the exact factorization of the electron-nuclear wave function, the coupling between electrons and nuclei beyond the adiabatic regime is encoded (i) in the time-dependent vector and scalar potentials and (ii) in the…
We present a detailed derivation and numerical tests of a new mixed quantum-classical scheme to deal with non-adiabatic processes. The method is presented as the zero-th order approximation to the exact coupled dynamics of electrons and…
We present a novel quantum-classical approach to non-adiabatic dynamics, deduced from the coupled electronic and nuclear equations in the framework of the exact factorization of the electron-nuclear wave function. The method is based on the…
We analyze the entanglement between electronic and nuclear motions in molecular wave functions, by using different widely used ansatzes in molecular Hamiltonian models (H$^+_2$ in 1D and the Shin-Metiu model); namely, i) Born-Oppenheimer…
The adiabatic Born-Oppenheimer approximation is considered to be a robust approach that very rarely breaks down. Consequently, it is predominantly utilized to address various electron-phonon properties in condensed matter physics. By…
We present a novel nonadiabatic perturbation theory (NAPT) for correlated systems of electrons and nuclei beyond the Born-Oppenheimer (BO) approximation. The essence of the method is to exploit the smallness of the electronic-to-nuclear…
In coupled cluster methods, the electronic states are biorthonormal in the sense that the left states are orthonormal to the right states. Here we present an extension of this formalism to a left and right total molecular wave function.…
Nonadiabatic corrections in molecules composed of a few atoms are considered. It is demonstrated that a systematic perturbative expansion around the adiabatic solution is possible, with the expansion parameter being the electron-nucleus…
We formulate a time-dependent density functional theory for the coupled dynamics of electrons and nuclei that goes beyond the Born-Oppenheimer (BO) approximation. We prove that the time-dependent marginal nuclear probability density…
It was recently shown that the exact potential driving the electron's dynamics in enhanced ionization of H$_2^+$ can have large contributions arising from dynamical electron-nuclear correlation, going beyond what any electrostatics-based…
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…
On-the-fly quantum nonadiabatic dynamics for large systems greatly benefits from the adiabatic representation readily available from the electronic structure programs. However, frequently occurring in this representation conical…