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The accuracy of reaction energy profiles calculated with multi-configurational electronic structure methods and corrected by multi-reference perturbation theory depends crucially on consistent active orbital spaces selected along the…

Chemical Physics · Physics 2023-04-14 Moritz Bensberg , Markus Reiher

An electrodynamical coupled cluster (CC) methodology starting from a covariant formalism and an equal time approximation, and finally based on the Dirac-Fock picture of the electron and positron fields and Coulomb gauge, is given here. The…

Atomic Physics · Physics 2019-04-30 Sambhu N. Datta

We present the concept, derivation, and implementation of dynamical configuration interaction, a quantum embedding theory that combines Green's function methodology with the many-body wave function. In a strongly-correlated active space, we…

Chemical Physics · Physics 2019-04-03 Marc Dvorak , Patrick Rinke

The accurate calculation of the (differential) correlation energy is central to the quantum chemical description of bond-formation and bond-dissociation processes. In order to estimate the quality of single- and multi-reference approaches…

Chemical Physics · Physics 2013-07-16 Katharina Boguslawski , Pawel Tecmer , Gergely Barcza , Ors Legeza , Markus Reiher

Coulomb interactions that occur in electronic structure calculations are correlated by allowing basis function components of the interacting densities to polarize, thereby reducing the magnitude of the interaction. Exchange integrals of…

Chemical Physics · Physics 2022-05-16 Jerry L. Whitten

Density functional theory with plane-wave basis sets is widely employed in computational materials science, including applications to isolated molecular systems. However, the inadequate description of electron correlation remains a…

Chemical Physics · Physics 2026-04-21 Qian Wang , Calvin Ku , Jyh-Pin Chou , Peng-Jen Chen , Alice Hu , Min-Hsiu Hsieh

The dipole moment is a crucial molecular property linked to a molecular system's bond polarity and overall electronic structure. To that end, the electronic dipole moment, which results from the electron density of a system, is often used…

In this work we propose a novel composite method for accurate calculation of the energies of many-electron atoms. The dominant contribution to the energy (pair energies) are calculated by using explicitly correlated factorisable coupled…

Atomic Physics · Physics 2018-12-12 Michal Przybytek , Michal Lesiuk

We have combined our adaptive configuration interaction (ACI) [J.B. Schriber and F.A. Evangelista, J. Chem. Phys. 144, 161106 (2016)] with a density-fitted implementation of the second-order perturbative multireference driven similarity…

Chemical Physics · Physics 2018-08-29 Jeffrey B. Schriber , Kevin P. Hannon , Francesco A. Evangelista

Wavefunctions restricted to electron-pair states are promising models to describe static/nondynamic electron correlation effects encountered, for instance, in bond-dissociation processes and transition-metal and actinide chemistry. To reach…

Chemical Physics · Physics 2017-01-18 Katharina Boguslawski , Paweł Tecmer

An accurate determination of the electron correlation energy is essential for describing the structure, stability, and function in a wide variety of systems, ranging from gas-phase molecular assemblies to condensed matter and…

Chemical Physics · Physics 2014-03-05 Alberto Ambrosetti , Anthony M. Reilly , Robert A. DiStasio , Alexandre Tkatchenko

We propose a descriptor for molecular electronic structure that is based solely on the one- and two-electron integrals but is translationally, rotationally, and unitarily invariant. Then, directly exploiting size consistency, we train and…

Quantum Physics · Physics 2026-03-02 Valerii Chuiko , Giovanni B. Da Rosa , Paul W. Ayers

The low-lying n(=3,4,5)d $^2D_{5/2}$ states alkaline earth ions are of vital importance in a number of different physical applications. The hyperfine structure constants of these states are characterized by unusually strong electron…

Atomic Physics · Physics 2015-06-26 B. K. Sahoo , C. Sur , T. Beier , B. P. Das , R. K. Chaudhuri , D. Mukherjee

State-of-the-art many-body wave function techniques rely on heuristics to achieve high accuracy at an attainable cost to solve the many-body Schr\"odinger equation. By far the most common property used to assess accuracy has been the total…

Chemical Physics · Physics 2022-11-30 Shunyue Yuan , Yueqing Chang , Lucas K. Wagner

We use continuum mechanics [Tao \emph{et al}, PRL{\bf 103},086401] to approximate the dynamic density response of interacting many-electron systems. Thence we develop a numerically efficient exchange-correlation energy functional based on…

Mesoscale and Nanoscale Physics · Physics 2012-08-28 Tim Gould , John F. Dobson

An explicitly orbital-dependent correlation energy functional is proposed, which is to be used in combination with the orbital-dependent exchange energy functional in energy-band calculations. It bears a close resemblance to the…

Strongly Correlated Electrons · Physics 2009-11-10 Masahiko Higuchi , Hiroshi Yasuhara

We present a method which computes many-electron energies and eigenfunctions by a full configuration interaction which uses a basis of atomistic tight-binding wave functions. This approach captures electron correlation as well as atomistic…

Mesoscale and Nanoscale Physics · Physics 2015-06-04 Erik Nielsen , Rajib Rahman , Richard P. Muller

A model subspace configuration interaction method is developed to obtain chemically accurate electron correlations by diagonalising a very compact effective Hamiltonian of realistic molecule. The construction of the effective Hamiltonian is…

Chemical Physics · Physics 2022-10-18 Jiasheng Li , Jun Yang

A new method that accurately describes strongly correlated states and captures dynamical correlation is presented. It is derived as a modification of coupled-cluster theory with single and double excitations (CCSD) through consideration of…

Chemical Physics · Physics 2013-07-15 Daniel Kats , Frederick R. Manby

The $\Delta$NO two-electron density matrix (2-RDM) and energy expression are derived from a multideterminantal wave function. The approximate $\Delta$NO 2-RDM is combined with an on-top density functional and a double-counting correction to…

Chemical Physics · Physics 2022-03-14 Ismael A. Elayan , Rishabh Gupta , Joshua W. Hollett