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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…

Chemical Physics · Physics 2024-05-07 Kalman Szenes , Maximilian Moerchen , Paul Fischill , Markus Reiher

The current work presents a new single-reference method for capturing at the same time the static and dynamic electron correlation. The starting-point is a determinant wavefunction formed with natural orbitals obtained from a new…

Chemical Physics · Physics 2017-08-16 Mario Piris

Accurately describing strong electron correlation in complex systems remains a prominent challenge in computational chemistry as near-term quantum algorithms treating total correlation often require prohibitively deep circuits. Here we…

Computational Engineering, Finance, and Science · Computer Science 2026-04-21 Zhanou Liu , Yuhao Chen , Yingjin Ma , Xiao He , Yuxin Deng

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

Quantum-chemical multi-configurational methods are required for a proper description of static electron correlation, a phenomenon inherent to the electronic structure of molecules with multiple (near-)degenerate frontier orbitals. Here, we…

Chemical Physics · Physics 2017-04-21 Christopher J. Stein , Markus Reiher

The tailored coupled cluster (TCC) approach is a promising ansatz that preserves the simplicity of single-reference coupled cluster theory, while incorporating a multi-reference wave function through amplitudes obtained from a preceding…

Chemical Physics · Physics 2021-01-07 Maximilian Mörchen , Leon Freitag , Markus Reiher

The account of electron correlation and its efficient separation into dynamic and nondynamic parts plays a key role in the development of computational methods. In this paper we suggest a physically-sound matrix formulation to split…

Chemical Physics · Physics 2016-08-16 Eloy Ramos-Cordoba , Pedro Salvador , Eduard Matito

Multi-configurational wave functions are known to describe electronic structure across a Born-Oppenheimer surface qualitatively correct. However, for quantitative reaction energies, dynamical correlation originating from the many…

Chemical Physics · Physics 2020-04-16 Christopher J. Stein , Markus Reiher

We present an efficient \textit{ab initio} method for calculating the electronic structure and total energy of strongly correlated electron systems. The method extends the traditional Gutzwiller approximation for one-particle operators to…

Strongly Correlated Electrons · Physics 2014-07-01 Y. X. Yao , J. Liu , C. Liu , W. C. Lu , C. Z. Wang , K. M. Ho

We present two efficient and intruder-free methods for treating dynamic correlation on top of general multi-configuration reference wave functions---including such as obtained by the density matrix renormalization group (DMRG) with large…

Chemical Physics · Physics 2016-09-13 Sandeep Sharma , Gerald Knizia , Sheng Guo , Ali Alavi

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

Quantitatively accurate electronic structure calculations rely on the proper description of electron correlation. A judicious choice of the approximate quantum chemistry method depends upon the importance of dynamic and nondynamic…

Chemical Physics · Physics 2019-05-09 Eloy Ramos-Cordoba , Eduard Matito

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

Wave functions based on electron-pair states provide inexpensive and reliable models to describe quantum many-body problems containing strongly-correlated electrons, given that broken-pair states have been appropriately accounted for by,…

Chemical Physics · Physics 2021-03-17 Artur Nowak , Ors Legeza , Katharina Boguslawski

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…

Chemical Physics · Physics 2018-09-05 Jerry L. Whitten

Some of the most spectacular failures of density-functional and Hartree-Fock theories are related to an incorrect description of the so-called static electron correlation. Motivated by recent progress on the N-representability problem of…

The $\Delta \text{NO}$ method for static correlation is combined with second-order M{\o}ller-Plesset perturbation theory (MP2) and coupled-cluster singles and doubles (CCSD) to account for dynamic correlation. The MP2 and CCSD expressions…

Chemical Physics · Physics 2020-06-05 Joshua W. Hollett , Pierre-François Loos

The choice that a solid system "makes" when adopting a crystal structure (stable or metastable) is ultimately governed by the interactions between electrons forming chemical bonds. By analyzing 6 prototypical binary transition-metal…

Strongly Correlated Electrons · Physics 2019-10-29 Nicola Lanatà , Tsung-Han Lee , Yong-Xin Yao , Vladan Stevanović , Vladimir Dobrosavljević

Electron correlations in molecules can be divided in short range dynamical correlations, long range Van der Waals type interactions and near degeneracy static correlations. In this work we analyze for a one-dimensional model of a…

Chemical Physics · Physics 2014-05-13 K. J. H. Giesbertz , R. van Leeuwen
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