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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…

Chemical Physics · Physics 2025-11-18 Jerry L. Whitten

High-precision atomic structure calculations require accurate modelling of electronic correlations typically addressed via the configuration interaction (CI) problem on a multiconfiguration wave function expansion. The latter can easily…

Atomic Physics · Physics 2023-06-22 Pavlo Bilous , Adriana Pálffy , Florian Marquardt

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

Selected configuration interaction (SCI) methods have emerged as state-of-the-art methodologies for achieving high accuracy and generating benchmark reference data for ground and excited states in small molecular systems. However, their…

Chemical Physics · Physics 2024-06-13 Hugh G. A. Burton , Pierre-François Loos

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 present a fully variational locally scaled self-interaction corrected (SIC) energy functional using complex optimal orbitals. This represents an important milestone for fully variational SIC energy functionals, which have been shown to…

Electronic resonances are metastable states that can decay by electron loss. They are ubiquitous across various fields of science, such as chemistry, physics, and biology. However, current theoretical and computational models for resonances…

Chemical Physics · Physics 2025-04-15 Yann Damour , Anthony Scemama , Fábris Kossoski , Pierre-François Loos

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…

A version of the configuration interaction (CI) method is developed which treats highly excited many-electron basis states perturbatively, so that their inclusion does not affect the size of the CI matrix. This removes, at least in…

Atomic Physics · Physics 2017-01-25 V. A. Dzuba , J. Berengut , C. Harabati , V. V. Flambaum

The Configuration Interaction (CI) method is applied to the calculation of the structures of a number of positron binding systems, including e+Be, e+Mg, e+Ca and e+Sr. These calculations were carried out in orbital spaces containing about…

Atomic Physics · Physics 2007-05-23 M. W. J. Bromley , J. Mitroy

Accuracy, variationality, and convergence underpin the reliability of modern electronic structure methods, yet definitive benchmarks in the relativistic regime remain elusive due to the absence of numerically exact full configuration…

Chemical Physics · Physics 2026-04-03 Shiv Upadhyay , Agam Shayit , Tianyuan Zhang , Stephen H. Yuwono , A. Eugene DePrince , Xiaosong Li

The cluster-in-molecule (CIM) local correlation approach with an accurate distant pair correlation energy correction is presented. For large systems, the inclusion of distant pair correlation energies is essential for the accurate…

Chemical Physics · Physics 2020-08-06 Zhigang Ni , Yang Guo , Frank Neese , Wei Li , Shuhua Li

Configuration-Interaction (CI) models are approximations to the electronic Schr\"odinger equation which are widely used for numerical electronic structure calculations in quantum chemistry. Based on our recent closed-form asymptotic results…

Mathematical Physics · Physics 2009-05-11 Gero Friesecke , Benjamin D. Goddard

It is often claimed that error cancellation plays an essential role in quantum chemistry and first-principle simulation for condensed matter physics and materials science. Indeed, while the energy of a large, or even medium-size, molecular…

Materials Science · Physics 2017-01-18 Eric Cancès , Geneviève Dusson

Adaptive atomistic/continuum (a/c) coupling method is an important method for the simulation of material and atomistic systems with defects to achieve the balance of accuracy and efficiency. Residual based a posteriori error estimator is…

Numerical Analysis · Mathematics 2022-11-28 Yangshuai Wang , Hao Wang

Configuration Interaction (CI) calculations on the ground state of the C atom are carried out using a small basis set of Slater orbitals [7s6p5d4f3g]. The configurations are selected according to their contribution to the total energy. One…

Atomic Physics · Physics 2017-08-01 María Belén Ruiz , Robert Tröger

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

We introduce and benchmark a systematically improvable route for excited-state calculations, state-specific configuration interaction ($\Delta$CI), \alert{which is a particular realization of multiconfigurational self-consistent field and…

Chemical Physics · Physics 2023-08-31 Fábris Kossoski , Pierre-François Loos

We apply the method of Monte Carlo configuration interaction (MCCI) to calculate ground-state potential energy curves for a range of small molecules and compare the results with full configuration interaction. We show that the MCCI…

Chemical Physics · Physics 2012-12-12 J. P. Coe , D. J. Taylor , M. J. Paterson

Defects on surfaces of semiconductors have a strong effect on their reactivity and catalytic properties. The concentration of different charge states of defects is determined by their formation energies. First-principles calculations are an…

Mesoscale and Nanoscale Physics · Physics 2017-07-05 Dmitry Vinichenko , M. Gokhan Sensoy , Cynthia M. Friend , Efthimios Kaxiras
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