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Methods for correcting residual energy errors of configuration interaction (CI) calculations of molecules and other electronic systems are discussed based on the assumption that the energy defect can be mapped onto atomic regions. The…

Chemical Physics · Physics 2022-10-05 Jerry L. Whitten

In this perspective, the various measures of electron correlation used in wavefunction theory, density functional theory and quantum information theory are briefly reviewed. We then focus on a more traditional metric based on dominant…

Chemical Physics · Physics 2023-04-07 Róbert Izsák , Aleksei V Ivanov , Nick S. Blunt , Nicole Holzmann , Frank Neese

Methods for estimating the correlation energy of molecules and other electronic systems are discussed based on the assumption that the correlation energy can be partitioned between atomic regions. In one method, the electron density is…

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

We investigate configuration-interaction (CI) calculations on a basis of molecular orbitals generated by preliminary density-functional theory (DFT) calculations. We use this CI/DFT framework to improve the modeling of core-excited states…

Chemical Physics · Physics 2025-09-11 Giorgio Visentin , Francois Mauger

The effect of the exchange-correlation potential in ab initio electron transport calculations is investigated by constructing optimized effective potentials (OEP) using different energy functionals or the electron density from second-order…

Mesoscale and Nanoscale Physics · Physics 2009-08-23 San-Huang Ke , Harold U. Baranger , Weitao Yang

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…

Quantum Physics · Physics 2012-12-18 Katharina Boguslawski , Paweł Tecmer , Örs Legeza , Markus Reiher

Accurate solution of the many-electron problem including correlations remains intractable except for few-electron systems. Describing interacting electrons as a superposition of independent electron configurations results in an apparent…

Computational Physics · Physics 2024-02-20 J. C. Greer

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

Multi-configurational approaches yield universal wave function parameterizations that can qualitatively well describe electronic structures along reaction pathways. For quantitative results, multi-reference perturbation theory is required…

Chemical Physics · Physics 2016-09-08 Christopher J. Stein , Vera von Burg , Markus Reiher

We demonstrate how to determine numerically nearly exact orthonormal orbitals that are optimal for evaluation of the energy of arbitrary (correlated) states of atoms and molecules by minimization of the energy Lagrangian. Orbitals are…

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

In the framework of ab initio dynamical mean field theory for realistic electronic structure calculations a new perturbation scheme which combine the T-matrix and fluctuating exchange approximations has been proposed. This method is less…

Strongly Correlated Electrons · Physics 2009-11-07 M. I. Katsnelson , A. I. Lichtenstein

We introduce the pCI software package for high-precision atomic structure calculations. The standard method of calculation is based on the configuration interaction (CI) method to describe valence correlations, but can be extended to attain…

In this paper, we propose an orbital iteration based parallel approach for electronic structure calculations. This approach is based on our understanding of the single-particle equations of independent particles that move in an effective…

Numerical Analysis · Mathematics 2014-11-06 Xiaoying Dai , Xingao Gong , Aihui Zhou , Jinwei Zhu

A new method to determine electron correlation energy is described. This method is based on a better representation of the potential due to interacting electrons that is obtained by specifying both the average and standard deviation. The…

Materials Science · Physics 2007-05-23 T. R. S. Prasanna

Correlation effects of an electron gas in an external potential are derived using an Effective Action functional method. Corrections beyond the random phase approximation (RPA) are naturally incorporated by this method. The Effective Action…

Materials Science · Physics 2009-11-10 A. Rebei , W. N. G. Hitchon

We consider electronic exchange and correlation effects in density-functional calculations of two-dimensional systems. Starting from wave function calculations of total energies and electron densities of inhomogeneous model systems, we…

Mesoscale and Nanoscale Physics · Physics 2012-05-30 Ilja Makkonen , Mikko M. Ervasti , Ville Kauppila , Ari Harju

Previous first-principles calculations of the melting properties of Si, based on the local-density approximation (LDA) for electronic exchange-correlation energy, under-predict the melting temperature by ~ 20%. We present new…

Materials Science · Physics 2016-08-16 D. Alfè , M. J. Gillan

An exchange-correlation energy functional beyond the local density approximation, based on the exchange-correlation kernel of the homogeneous electron gas and originally introduced by Kohn and Sham, is considered for electronic structure…

Condensed Matter · Physics 2016-08-31 Maurizia Palummo , Giovanni Onida , Rodolfo Del Sole

We establish a link between quantum mechanical molecular simulations and the transfer matrix of a molecule. The transfer matrix (T-matrix) of an object provides a complete description of its electromagnetic response. Once the T-matrices of…

Chemical Physics · Physics 2020-04-21 Ivan Fernandez-Corbaton , Carsten Rockstuhl , Wim Klopper
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