Where Does Electron Correlation Lie? Some Answers from a Real Space Partition

José Luis Casalz-Sainz; José Manuel Guevara-Vela; Evelio Francisco; Tomás Rocha-Rinza; Ángel Martín Pendás

doi:10.1002/cphc.201700940

Where Does Electron Correlation Lie? Some Answers from a Real Space Partition

José Luis Casalz-Sainz
, José Manuel Guevara-Vela
, Evelio Francisco
, Tomás Rocha-Rinza
, Ángel Martín Pendás^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

27 Citations (Scopus)

Abstract

We discuss an intra- and interatomic partition of the electron correlation energy (E_corr) within the interacting quantum atoms (IQA) approach at the accurate coupled cluster level with single, double, and estimated triple excitations (CCSDT(T)). This division offers a privileged window into the spatial localization of this component of the molecular energy. We show that the total molecular E_corr is dominated by the intra-atomic or intra-fragment terms and that interatomic contributions change smoothly from short- to long-range correlation (dispersion). The sign of these interatomic correlation terms differentiate between (i) mainly covalent or (ii) mainly ionic or nonbonded interactions. We propose that this feature may be used to define and examine intramolecular dispersion terms.

Original language	English
Pages (from-to)	3553-3561
Number of pages	9
Journal	ChemPhysChem
Volume	18
Issue number	24
DOIs	https://doi.org/10.1002/cphc.201700940
Publication status	Published - 15 Dec 2017

Keywords

ab initio calculations
bond theory
electron localization
electronic structures
noncovalent interactions

ASJC Scopus subject areas

Atomic and Molecular Physics, and Optics
Physical and Theoretical Chemistry

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10.1002/cphc.201700940

Cite this

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abstract = "We discuss an intra- and interatomic partition of the electron correlation energy (Ecorr) within the interacting quantum atoms (IQA) approach at the accurate coupled cluster level with single, double, and estimated triple excitations (CCSDT(T)). This division offers a privileged window into the spatial localization of this component of the molecular energy. We show that the total molecular Ecorr is dominated by the intra-atomic or intra-fragment terms and that interatomic contributions change smoothly from short- to long-range correlation (dispersion). The sign of these interatomic correlation terms differentiate between (i) mainly covalent or (ii) mainly ionic or nonbonded interactions. We propose that this feature may be used to define and examine intramolecular dispersion terms.",

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AU - Casalz-Sainz, José Luis

AU - Guevara-Vela, José Manuel

AU - Francisco, Evelio

AU - Rocha-Rinza, Tomás

AU - Martín Pendás, Ángel

PY - 2017/12/15

Y1 - 2017/12/15

N2 - We discuss an intra- and interatomic partition of the electron correlation energy (Ecorr) within the interacting quantum atoms (IQA) approach at the accurate coupled cluster level with single, double, and estimated triple excitations (CCSDT(T)). This division offers a privileged window into the spatial localization of this component of the molecular energy. We show that the total molecular Ecorr is dominated by the intra-atomic or intra-fragment terms and that interatomic contributions change smoothly from short- to long-range correlation (dispersion). The sign of these interatomic correlation terms differentiate between (i) mainly covalent or (ii) mainly ionic or nonbonded interactions. We propose that this feature may be used to define and examine intramolecular dispersion terms.

AB - We discuss an intra- and interatomic partition of the electron correlation energy (Ecorr) within the interacting quantum atoms (IQA) approach at the accurate coupled cluster level with single, double, and estimated triple excitations (CCSDT(T)). This division offers a privileged window into the spatial localization of this component of the molecular energy. We show that the total molecular Ecorr is dominated by the intra-atomic or intra-fragment terms and that interatomic contributions change smoothly from short- to long-range correlation (dispersion). The sign of these interatomic correlation terms differentiate between (i) mainly covalent or (ii) mainly ionic or nonbonded interactions. We propose that this feature may be used to define and examine intramolecular dispersion terms.

KW - ab initio calculations

KW - bond theory

KW - electron localization

KW - electronic structures

KW - noncovalent interactions

UR - https://www.scopus.com/pages/publications/85038594435

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DO - 10.1002/cphc.201700940

M3 - Article

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AN - SCOPUS:85038594435

SN - 1439-4235

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EP - 3561

JO - ChemPhysChem

JF - ChemPhysChem

IS - 24

ER -

Where Does Electron Correlation Lie? Some Answers from a Real Space Partition

Abstract

Keywords

ASJC Scopus subject areas

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