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Molecular QTAIM Topology Is Sensitive to Relativistic Corrections
Author(s) -
Anderson James S. M.,
Rodríguez Juan I.,
Ayers Paul W.,
TrujilloGonzález Daniel E.,
Götz Andreas W.,
Autschbach Jochen,
CastilloAlvarado Fray L.,
Yamashita Koichi
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201804464
Subject(s) - relativistic quantum chemistry , topology (electrical circuits) , atoms in molecules , physics , electron , atomic physics , chemistry , quantum mechanics , mathematics , combinatorics
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.