Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

James S.M. Anderson; Juan I. Rodríguez; Paul W. Ayers; Daniel E. Trujillo-González; Andreas W. Götz; Jochen Autschbach; Fray L. Castillo-Alvarado; Koichi Yamashita

doi:10.1002/chem.201804464

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

James S.M. Anderson, Juan I. Rodríguez, Paul W. Ayers, Daniel E. Trujillo-González, Andreas W. Götz, Jochen Autschbach, Fray L. Castillo-Alvarado, Koichi Yamashita

Escuela Superior de Física y Matemáticas (ESFM)

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

9 Scopus citations

Abstract

The topology of the molecular electron density of benzene dithiol gold cluster complex Au ₄ −S−C ₆ H ₄ −S′−Au′ ₄ changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.

Original language	English
Pages (from-to)	2538-2544
Number of pages	7
Journal	Chemistry - A European Journal
Volume	25
Issue number	10
DOIs	https://doi.org/10.1002/chem.201804464
State	Published - 18 Feb 2019

Keywords

Amsterdam density functional
computational chemistry
quantum theory of atoms in molecules
topology

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10.1002/chem.201804464

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title = "Molecular QTAIM Topology Is Sensitive to Relativistic Corrections",

abstract = " The topology of the molecular electron density of benzene dithiol gold cluster complex Au 4 −S−C 6 H 4 −S′−Au′ 4 changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.",

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T1 - Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

AU - Anderson, James S.M.

AU - Rodríguez, Juan I.

AU - Ayers, Paul W.

AU - Trujillo-González, Daniel E.

AU - Götz, Andreas W.

AU - Autschbach, Jochen

AU - Castillo-Alvarado, Fray L.

AU - Yamashita, Koichi

PY - 2019/2/18

Y1 - 2019/2/18

N2 - The topology of the molecular electron density of benzene dithiol gold cluster complex Au 4 −S−C 6 H 4 −S′−Au′ 4 changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.

AB - The topology of the molecular electron density of benzene dithiol gold cluster complex Au 4 −S−C 6 H 4 −S′−Au′ 4 changed when relativistic corrections were made and the structure was close to a minimum of the Born–Oppenheimer energy surface. Specifically, new bond paths between hydrogen atoms on the benzene ring and gold atoms appeared, indicating that there is a favorable interaction between these atoms at the relativistic level. This is consistent with the observation that gold becomes a better electron acceptor when relativistic corrections are applied. In addition to relativistic effects, here, we establish the sensitivity of molecular topology to basis sets and convergence thresholds for geometry optimization.

KW - Amsterdam density functional

KW - computational chemistry

KW - quantum theory of atoms in molecules

KW - topology

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DO - 10.1002/chem.201804464

M3 - Artículo

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SP - 2538

EP - 2544

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 10

ER -

Molecular QTAIM Topology Is Sensitive to Relativistic Corrections

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