Related papers: Nonadiabatic Potential Energy Surfaces For A Molec…
We present a model intended for rapid sampling of ground and excited state potential energy surfaces for first-row transition metal active sites. The method is computationally inexpensive and is suited for dynamics simulations where (1)…
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…
Non-adiabatic effects play an important role in many chemical processes. In order to study the underlying non-adiabatic potential-energy surfaces (PESs), we present a locally-constrained density-functional theory approach, which enables us…
Accurate and efficient simulation of excited state properties is an important and much aspired cornerstone in the study of adsorbate dynamics on metal surfaces. To this end, the recently proposed linear expansion \Delta Self-Consistent…
We derive and implement analytic nuclear gradients and derivative couplings for a constrained Complete Active Space Self-Consistent Field with a small active space designed to model electron or hole transfer. Using a Lagrangian formalism,…
We present a modification of the $\Delta$SCF method of calculating energies of excited states, in order to make it applicable to resonance calculations of molecules adsorbed on metal surfaces, where the molecular orbitals are highly…
State-specific complete active space self-consistent field (SS-CASSCF) theory has emerged as a promising route to accurately predict electronically excited energy surfaces away from molecular equilibria. However, its accuracy and…
We extend ground-state density-functional theory to excited states and provide the theoretical formulation for the widely used $\Delta SCF$ method for calculating excited-state energies and densities. As the electron density alone is…
A general approach to calculate the diabatic surfaces for electron-transfer reactions is presented, based on first-principles molecular dynamics of the active centers and their surrounding medium. The excitation energy corresponding to the…
Surface hopping algorithms, as an important class of quantum dynamics simulation algorithms for non-adiabatic dynamics, are typically performed in the adiabatic representation, which can break down in the presence of ill-defined adiabatic…
To describe excited states, the electron density alone being insufficient, we use the noninteracting reference density matrix $\gamma_{s}({\bf x},{\bf x}')$ based on the recently established foundation for the $\Delta SCF$ theory, in which…
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…
We present a model for Desorption Induce by (Multiple) Electronic Transitions (DIET/DIMET) based on potential energy surfaces calculated with the Delta Self-Consistent Field extension of Density Functional Theory. We calculate potential…
We prove the general chemical potential theorem: the noninteracting one-electron orbital energies in DFT ground states and $\Delta$SCF excited states are corresponding chemical potentials of electron addition or removal, from an…
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…
We compute highly accurate first principle based \textit{ab initio} adiabatic potential energy surfaces (PESs) using State-Averaged Multi-Configurational Self-Consistent Field (SA-MCSCF) followed by internally contracted Multi-Reference…
Multi-dimensional constrained covariant density functional theories were developed recently. In these theories, all shape degrees of freedom \beta_{\lambda\mu} deformations with even \mu are allowed, e.g., \beta_{20}, \beta_{22},…
We investigate active electrolytes within the mean-field level of description. The focus is on how the double-layer structure of passive, thermalized charges is affected by active dynamics of all constituting ions. One feature of active…
We test a set of multiconfigurational wavefunction approaches for calculating the ground state electron population for a two-site Anderson model representing a molecule on a metal surface. In particular, we compare (i) a Hartree Fock like…
This paper presents two new adiabatic, global potential energy surfaces (PESs) for the two lowest $^3A'$ and $^3A''$ electronic states of the O($^3P$)+H$_2$ system. For each of these states, ab initio electronic energies were calculated for…