Related papers: On Corrections to the Born-Oppenheimer Approximati…
Electron transfer is an important and fundamental process in chemistry, biology and physics, and has received significant attention in recent years. Perhaps one of the most intriguing questions concerns with the realization of the…
This paper presents the calculation of the electric transition dipole moment in a pre-Born-Oppenheimer framework. Electrons and nuclei are treated equally in terms of the parametrization of the non-relativistic total wave function, which is…
We analyse a nonadiabatic self-consistent field method by means of an exactly-solvable model. The method is based on nuclear and electronic orbitals that are functions of the cartesian coordinates in the laboratory-fixed frame. The kinetic…
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…
With the recent advances in the development of devices capable of performing quantum computations, a growing interest in finding near-term applications has emerged in many areas of science. In the era of non-fault tolerant quantum devices,…
An attractive way to model nuclear quantum effects is to describe select nuclei quantum mechanically at the same level as the electrons. This non-Born-Oppenheimer (non-BO) method is known by many names including the nuclear-electronic…
We propose an alternative to the usual time--independent Born--Oppenheimer approximation that is specifically designed to describe molecules with non--symmetrical hydrogen bonds. In our approach, the masses of the hydrogen nuclei are scaled…
We present an alternative one-electron equation for resolving many-electron problem to one-electron approximation and including the exchange and correlation effects in an analytical way, thereby fulfilling the requirements for ab initio…
The leading nonadiabatic corrections to rovibrational levels of a diatomic molecule are expressed in terms of three functions of internuclear distance: corrections to the adiabatic potential, the effective nuclear mass, and the effective…
Quantum trajectory calculations for electrons are a useful tool in the field of molecular dynamics, e.g. to understand processes in ultrafast spectroscopy. They have, however, two limitation: On the one hand, such calculations are typically…
With recent developments in simulating nonadiabatic systems to high accuracy, it has become possible to determine how much energy is attributed to nuclear quantum effects beyond zero-point energy. In this work we calculate the…
We study non--adiabatic transitions in scattering theory for the time dependent molecular Schroedinger equation in the Born--Oppenheimer limit. We assume the electron Hamiltonian has finitely many levels and consider the propagation of…
Non-adiabatic molecular phenomena, arising from the breakdown of the Born-Oppenheimer approximation, govern the fate of virtually all photo-physical and photochemical processes and limit the quantum efficiency of molecules and other…
We consider non-adiabatic transitions in multiple dimensions, which occur when the Born-Oppenheimer approximation breaks down. We present a general, multi-dimensional algorithm which can be used to accurately and efficiently compute the…
In radiation damage cascade displacement spikes ions and electrons can reach very high temperatures and be out of thermal equilibrium. Correct modelling of cascades with molecular dynamics should allow for the non-adiabatic exchange of…
It was recently shown [G. Albareda, et al., Phys. Rev. Lett. 113, 083003 (2014)] that within the conditional decomposition approach to the coupled electron-nuclear dynamics, the electron-nuclear wave function can be exactly decomposed into…
In order to interpret precise measurements of molecular properties the finite nuclear mass corrections to the Born-Oppenheimer approximation have to be accounted for. It is shown that they can be obtained systematically in the perturbative…
The quantum electrodynamic Araki-Sucher correction arising from the interaction between electrons and nuclei is calculated for rovibrational energy levels of the hydrogen molecule and its isotopologues. The corresponding expectation value…
We study linear problems of mathematical physics in which the adiabatic approximation is used in the wide sense. Using the idea that all these problems can be treated as problems with operator-valued symbol, we propose a general regular…
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…