Related papers: The Delicate Balance of Static and Dynamic Electro…
A method for increasing the accuracy of configuration interaction (CI) calculations of molecules and other electronic systems is proposed. The energy defect of a given calculation is associated with the electron pair origin of…
A proper theoretical description of electronic structure of the 3d orbitals in the metal centers of functional metalorganics is a challenging problem. In this letter, we apply density functional theory and an exact diagonalization method in…
Orbital entropies, pair entropies, and mutual information have become popular tools for analysis of strongly correlated wave functions. They can quantitatively measure how strongly an orbital (e.g. from the DMRG active space) participates…
An ab initio approach formulated under an entropy-inspired repartitioning of the electronic Hamiltonian is presented. This ansatz produces orbital eigenvalues each shifted by entropic contributions expressed as subsets of scaled pair…
We present a novel method that appropriately handles both dynamical and static electron correlation in a balanced manner, using a perturbation theory on a spin-extended Hartree-Fock (EHF) wave function reference. While EHF is a suitable…
Efficiently recovering dynamic correlation in strongly correlated systems without incurring prohibitive computational costs remains a central challenge in quantum chemistry. In this Perspective, we review and benchmark methods capable of…
Most nonrelativistic electron correlation methods can be adapted to account for relativistic effects, as long as the relativistic molecular spinor integrals are available, from either a four-, two-, or one-component mean-field calculation.…
Electronic correlation is a complex many-body effect and the correlation energy depends on the specific electronic structure and spatial distribution of electrons in each atom and molecule. Although the total correlation energy in an atom…
Adiabatic mixed quantum/classical molecular dynamics simulations were used to generate snapshots of the hydrated electron (e-) in liquid water at 300 K. Water cluster anions that include two complete solvation shells centered on the e- were…
We propose a multiconfigurational hybrid density-functional theory which rigorously combines a multiconfiguration self-consistent-field calculation with a density-functional approximation based on a linear decomposition of the…
Solid state physics deals with systems composed of atoms with strongly bound electrons. The tunneling probability of each electron is determined by interactions that typically extend to neighboring sites, as their corresponding wave…
Accurate charge densities are essential for reliable electronic structure calculations because they significantly impact predictions of various chemical properties and in particular, according to the Hellmann-Feynman theorem, atomic forces.…
An accurate description of strong correlation is quintessential for the exploration of emerging chemical phenomena. While near-term variational quantum algorithms provide a theoretically scalable framework for quantum chemical problems, the…
We present an efficient approach to the electron correlation problem that is well-suited for strongly interacting many-body systems, but requires only mean-field-like computational cost. %which is based on orbital optimization of electron…
In order to explore the effects of high levels of electron correlation on the real-time coupled cluster formalism and algorithmic behavior, we introduce a time-dependent implementation of the CC3 singles, doubles and approximate triples…
Unitary Coupled Cluster (UCC) theory is a promising variational method for electronic structure calculations, especially for strongly correlated systems and quantum computers. However, its practical application is limited by the steep…
We present an information-theoretic assessment of atomic and molecular densities in the ground state and under a range of physical scenarios--excitation, confinement, and ensemblization. Comparisons across densities obtained from…
The dynamic response of an interacting electron system is determined by an extension of the relaxation-time approximation forced to obey local conservation laws for number, momentum and energy. A consequence of these imposed constraints is…
We investigate the impact of dissipation on the energy balance in the electron dynamics of metal clusters excited by strong electro-magnetic pulses. The dynamics is described theoretically by Time-Dependent Density-Functional Theory (TDDFT)…
Wavefunctions constructed from electron-pair states can accurately model strong electron correlation effects and are promising approaches especially for larger many-body systems. In this article, we analyze the nature and the type of…