Local descriptors of dynamic and nondynamic correlation

Abstract

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 correlation, which is usually assessed by scalar measures. Existing measures of electron correlation do not consider separately the regions of the Cartesian space where dynamic or nondynamic correlation are most important. We introduce real-space descriptors of dynamic and nondynamic electron correlation that admit orbital decomposition. Integration of the local descriptors yields global numbers that can be used to quantify dynamic and nondynamic correlation. Illustrative examples over different chemical systems with varying electron correlation regimes are used to demonstrate the capabilities of the local descriptors. Since the expressions only require orbitals and occupation numbers, they can be readily applied in the context of local correlation methods, hybrid methods, density matrix functional theory and fractional-occupancy density functional theory.

References in corpus (10)

• Density functional theory with fractional orbital occupations
• Entanglement Measures for Single- and Multi-Reference Correlation Effects
• Can single-reference coupled cluster theory describe static correlation?
• Separation of Dynamic and Nondynamic Correlation
• Thermally-assisted-occupation density functional theory with generalized-gradient approximations
• The correlation theory of the chemical bond
• On the exact formulation of multi-configuration density-functional theory: electron density versus orbitals occupation
• Robust Validation Of Approximate 1-Matrix Functionals With Few-Electron Harmonium Atoms
• H${}_4$: A Challenging System For Natural Orbital Functional Approximations
• Fermi and Coulomb correlation effects upon the interacting quantum atoms energy partition

Cited by in corpus (10)

• The MOBH35 metal-organic barrier heights reconsidered: performance of local-orbital coupled cluster approaches in different static correlation regimes
• Putting Density Functional Theory to the Test in Machine-Learning-Accelerated Materials Discovery
• Singling Out Dynamic and Nondynamic Correlation
• Measuring Electron Correlation. The Impact of Symmetry and Orbital Transformations
• Partition of Optical Properties Into Orbital Contributions
• Range separation of the Coulomb hole
• The Coulomb Hole of the Ne atom
• The Wigner localization of interacting electrons in a one-dimensional harmonic potential
• Time-Reversal Symmetry in RDMFT and pCCD with Complex-Valued Orbitals
• Graphic characterization and clustering configuration descriptors of determinant space for molecules