Related papers: On Corrections to the Born-Oppenheimer Approximati…
The choice of the electronic representation in on-the-fly quantum dynamics is crucial. The adiabatic representation is appealing since adiabatic states are readily available from quantum chemistry packages. The nuclear wavepackets are then…
A novel mixed quantum-classical approach to simulating nonadiabatic dynamics of molecules at metal surfaces is presented. The method combines the numerically exact hierarchical equations of motion approach for the quantum electronic degrees…
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…
This work presents an alternative, general, and in-principle exact extension of electronic Kohn-Sham density functional theory (KS-DFT) to the fully quantum-mechanical molecular problem. Unlike in existing multi-component or…
The adiabatic approximation has formed the basis for much of our understandings of the interaction of light and electrons. The classical non-recoil approximation or quantum mechanical Wolkow states of free electron waves have been routinely…
In order to understand quantum decoherence of a quantum system due to its interaction with a large system behaving classically, we introduce the concept of adiabatic quantum entanglement based on the Born-Oppenhemeir approximation. In the…
The molecular junction geometry is modelled in terms of nuclear degrees of freedom that are embedded in a stochastic quantum environment of non-equilibrium electrons. Time-evolution of the molecular geometry is governed via a mean force, a…
The newly developed nonadiabatic method based on the coupled-channel Schroedinger equation with Gamow states is used to study the phenomenon of proton radioactivity. The new method, adopting the weak coupling regime of the…
We propose a general approach to reducing basis set incompleteness error in electron correlation energy calculations. The correction is computed alongside the correlation energy in a single calculation by modifying the electron interaction…
Accurate simulation of the non-adiabatic dynamics of molecules in excited electronic states is key to understanding molecular photo-physical processes. Here we present a novel method, based on a semiclassical approximation, that is as…
Photoionization using attosecond pulses can lead to the formation of coherent superpositions of the electronic states of the parent ion. However, ultrafast electron ejection triggers not only electronic but also nuclear dynamics---leading…
Based on quantum reactive-scattering theory, we propose a method for studying the electronic nonadiabaticity in collision processes involving electron-ion rearrangements. We investigate the state-to-state transition probability for…
The decomposition of electronic and nuclear motion presented in~[A. Abedi, N. T. Maitra, and E. K. U. Gross, Phys. Rev. Lett. 105, 123002 (2010)] yields a time-dependent potential that drives the nuclear motion and fully accounts for the…
We develop a unified quantum geometric framework to understand reactive quantum dynamics. The critical roles of the quantum geometry of adiabatic electronic states in both adiabatic and non-adiabatic quantum dynamics are unveiled. A…
Modeling many-body quantum systems with strong interactions is one of the core challenges of modern physics. A range of methods has been developed to approach this task, each with its own idiosyncrasies, approximations, and realm of…
We investigate the quantum mechanics of a single particle constrained to move along an arbitrary smooth reference curve by a confinement that is allowed to vary along the waveguide. The Schr\"odinger equation is evaluated in the adapted…
The recent improvement in experimental capabilities for interrogating and controlling molecular systems with ultrafast coherent light sources calls for the development of theoretical approaches that can accurately and efficiently treat…
An extension of the CCS-method [Chem. Phys. 2004, 304, p. 103-120] for simulating non-adiabatic dynamics with quantum effects of the nuclei is put forward. The time-dependent Schr\"{o}dinger equation for the motion of the nuclei is solved…
Relativistic, quantum electrodynamics, as well as non-adiabatic corrections and couplings, are computed for the b $^3\Pi_\mathrm{g}$ and c $^3\Sigma_\mathrm{g}^+$ electronic states of the helium dimer. The underlying Born-Oppenheimer…
Structural phase transitions are accompanied by a movement of one nucleus (or a few) in the crystallographic unit cell. If the nucleus movement is continuous, a second order phase transition without latent heat results, whereas an abrupt…