A Topological Data Analysis perspective on noncovalent interactions in relativistic calculations

Topological Data Analysis (TDA) is a powerful mathematical theory, largely unexplored in theoretical chemistry. In this work we demonstrate how TDA provides new insights into topological features of electron densities and reduced density gradients, by investigating the effects of relativity on the b...

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Bibliographic Details
Published in:International journal of quantum chemistry 2020-04, Vol.120 (8), p.n/a
Main Authors: Olejniczak, Małgorzata, Severo Pereira Gomes, André, Tierny, Julien
Format: Article
Language:English
Subjects:
Chemical bonds
Chemistry
Data analysis
Density gradients
Electron density
Electronic structure
Hydrogen atoms
noncovalent interactions
Organic chemistry
Physical chemistry
quantum chemistry
Quantum physics
Quantum theory
Relativism
Relativistic effects
Relativity
Structural analysis
Topological Data Analysis
Topology
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Summary:Topological Data Analysis (TDA) is a powerful mathematical theory, largely unexplored in theoretical chemistry. In this work we demonstrate how TDA provides new insights into topological features of electron densities and reduced density gradients, by investigating the effects of relativity on the bonding of the Au4‐S‐C6H4‐S′‐Au′4 molecule. Whereas recent analyses of this species carried out with the Quantum Theory of Atoms‐In‐Molecules (a previous study) concluded, from the emergence of new topological features in the electron density, that relativistic effects yielded noncovalent interactions between gold and hydrogen atoms, we show from their low persistence values (which decrease with increased basis set size) these features are not significant. Further analysis of the reduced density gradient confirms no relativity‐induced noncovalent interactions in Au4‐S‐C6H4‐S′‐Au′4. We argue TDA should be integrated into electronic structure analysis methods, and be considered as a basis for the development of new topology‐based approaches. Topological features of the electron density can be quantified by persistence—a measure used in the Topological Data Analysis. It is shown that the analysis of persistence can be used to reinvestigate the role of relativistic effects on the emergence of noncovalent interactions in selected gold complexes. This article also advocates for the inclusion of the Topological Data Analysis in a quantum chemistry toolbox.
ISSN:0020-7608
1097-461X
DOI:10.1002/qua.26133