Related papers: Using molecular similarity to construct accurate s…
Multi-configurational electronic structure theory delivers the most versatile approximations to many-electron wavefunctions, flexible enough to deal with all sorts of transformations, ranging from electronic excitations, to open-shell…
We study model one-dimensional chemical systems (representative of their three-dimensional counterparts) using the strictly-correlated electrons (SCE) functional, which, by construction, becomes asymptotically exact in the limit of infinite…
We extend density matrix embedding theory to periodic systems, resulting in an electronic band structure method for solid-state materials. The electron correlation can be captured by means of a local impurity model using various choices of…
We present a novel theory and implementation for computing coupled electronic and quantal nuclear subsystems on a single potential energy surface, moving beyond the standard Born-Oppenheimer (BO) separation of nuclei and electrons. We…
Explicit-electron force fields introduce electrons or electron pairs as semi-classical particles in force fields or empirical potentials, which are suitable for molecular dynamics simulations. Even though semi-classical electrons are a…
We introduce an energy functional for ground-state electronic structure calculations. Its variables are the natural spin-orbitals of singlet many-body wave functions and their joint occupation probabilities deriving from controlled…
We present a new theory for partitioning simulations of periodic and solid-state systems into physically sound atomic contributions at the level of Kohn-Sham density functional theory. Our theory is based on spatially localized linear…
The complex nature of electron-electron correlations is made manifest in the very simple but non-trivial problem of two electrons confined within a sphere. The description of highly non-local correlation and self-interaction effects by…
An outstanding challenge in chemical computation is the many-electron problem where computational methodologies scale prohibitively with system size. The energy of any molecule can be expressed as a weighted sum of the energies of…
The correlation energies of the helium isoelectronic sequence and of Hooke's atom isoelectronic sequence have been evaluated using an assortment of local, gradient and meta-gradient density functionals. The results are compared with the…
We prove that the electron density function of a real physical system can be uniquely determined by its values on any finite subsystem. This establishes the existence of a rigorous density-functional theory for any open electronic system.…
Exposing a molecule to intense light pulses may bring this molecule to a nonstationary quantum state, thus launching correlated dynamics of electronic and nuclear subsystems. Although much had been achieved in the understanding of…
Electron correlation effects are essential for an accurate ab initio description of molecules. A quantitative a priori knowledge of the single- or multi-reference nature of electronic structures as well as of the dominant contributions to…
In this work, we present a new computational approach to characterize and classify molecular packing in the solid states. The key idea is to project each neighboring molecule (or short contact) from the centered molecule into a unit sphere…
New ways to treat electron correlation in electronic structure problems are discussed in the context of many-electron theory. The present work focuses primarily on static correlation. In related work, a method for including dynamical…
Multipole moments are the first order responses of the energy to spatial derivatives of the electric field strength. The quality of density functional theory (DFT) prediction of molecular multipole moments thus characterizes errors in…
Electron transfer with changing occupation in the 4f subshell poses a considerable challenge for quantitative predictions in quantum chemistry. Using the example of cerium oxide, we identify the main deficiencies of common…
Accurately treating strong electron correlation in quantum chemistry typically requires multireference wave-function methods with steep computational scaling. The recently proposed i-DMFT method promises near configuration-interaction…
The exact universal functional of integer charge leads to an extension to fractional charge asymptotically when it is applied to a system made of asymptotically separated densities. The extended functional is asymptotically local and is…
We introduce a novel energy functional for ground-state electronic-structure calculations. Its fundamental variables are the natural spin-orbitals of the implied singlet many-body wave function and their joint occupation probabilities. The…