相关论文: Electron Transfer, Diabatic Couplings and Vibronic…
We present a novel semiclassical phase-space surface hopping approach that goes beyond the Born-Oppenheimer approximation and all existing surface hopping formalisms. We demonstrate that working with a correct phase-space electronic…
Marcus--Hush theory explains electron transfer in terms of reorganization energies, driving forces, electronic couplings, and reduced free-energy or energy-gap descriptions. These descriptions do not by themselves determine when the…
Phase-space electronic structure theory offers up a new and powerful approach for tackling problems with coupled nuclear-electronic dynamics in a fashion that goes beyond Born-Oppenheimer (BO) theory. Whereas BO theory stipulates that we…
Accurate description of nonadiabatic dynamics of molecules at metal surfaces involving electron transfer has been a longstanding challenge for theory. Here, we tackle this problem by first constructing high-dimensional neural network…
We show that following the standard mantra of quantum chemistry and diagonalizing the Born-Oppenheimer (BO) Hamiltonian $\hat H_{\rm BO}(\bm R)$ is not the optimal means to construct potential energy surfaces. A better approach is to…
Experimental observations of multi-quantum relaxation of highly vibrationally excited NO scattering from Au(111) are a benchmark for the breakdown of Born-Oppenheimer approximation in molecule-surface systems. This remarkable vibrational…
Based on the reduced density matrix method, we compare two different approaches to calculate the dynamics of the electron transfer in systems with donor, bridge, and acceptor. In the first approach a vibrational substructure is taken into…
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…
Energy transfer during molecular collisions on metal surfaces plays a pivotal role in a host of critical interfacial processes. Despite significant efforts, our understanding of relevant energy transfer mechanisms, even in an…
We theoretically analyzed inelastic effects in the electron transport through molecular junctions originating from electron-vibron interactions. The molecular bridge was simulated by a periodic chain of identical interacting hydrogen-like…
A review of the present state of investigations of the pseudospin-electron model (PEM), which is used in the theory of strongly correlated electron systems, is given. The model is used to describe the systems with the locally anharmonic…
We present a phase-space electronic Hamiltonian $\hat{H}_{PS}$ (parameterized by both nuclear position $\mathbf{X}$ and momentum $\mathbf{P}$) that boosts each electron into the moving frame of the nuclei that are closest in real space --…
A process of energy transfer is demonstrated in non-equilibrium charged particle beams with anisotropy and space charge. Equipartitioning of energy between available degrees of freedom occurs in just a few betatron wavelengths, without halo…
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…
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…
We explore the classical dynamics of two interacting rotating dipoles that are fixed in the space and exposed to an external homogeneous electric field. Kinetic energy transfer mechanisms between the dipoles are investigated varying both…
Modern electronic structure theory is built around the Born-Oppenheimer approximation and the construction of an electronic Hamiltonian H_{el}(X) that depends on the nuclear position X (and not the nuclear momentum P). In this article,…
We consider an electron constrained to move on a surface with revolution symmetry in the presence of a constant magnetic field $B$ parallel to the surface axis. Depending on $B$ and the surface geometry the transverse part of the spectrum…
Bridge-mediated electron transfer (ET) between a donor and an acceptor is prototypical for the description of numerous most important ET scenarios. While multi-step ET and the interplay of sequential and direct superexchange transfer…
We recently proposed effective normal modes for excitonically coupled aggregates which exactly transform the energy transfer Hamiltonian into a sum of one-dimensional Hamiltonians along the effective normal modes. Identifying physically…