Assessment of scalar relativistic effects on halogen bonding and σ‐hole properties
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F20%3A43920256" target="_blank" >RIV/60461373:22340/20:43920256 - isvavai.cz</a>
Result on the web
<a href="https://doi.org/10.1002/qua.26392" target="_blank" >https://doi.org/10.1002/qua.26392</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/qua.26392" target="_blank" >10.1002/qua.26392</a>
Alternative languages
Result language
angličtina
Original language name
Assessment of scalar relativistic effects on halogen bonding and σ‐hole properties
Original language description
Halogen bond (X‐bond) is a noncovalent interaction between a halogen atom and an electron donor. It is often rationalized by a region of the positive electrostatic potential on the halogen atom, so‐called σ‐hole. The X‐bond strength increases with the atomic number of the halogen involved; thus, for heavier halogens, relativistic effects become of concern. This poses a challenge for the quantum chemical description of X‐bonded complexes. To quantify scalar relativistic effects (SREs) on the interaction energies and σ‐hole properties, we have performed highly accurate coupled‐cluster calculations at the complete basis set limit of several X‐bonded complexes and their halogenated monomers. We found that the SREs are comparable in magnitude to the effect of the basis set. The nonrelativistic calculations typically underestimate the attraction by up to 5% or 23% for brominated and iodinated complexes, respectively. Counterintuitively, the electron densities at the bond critical points are larger for SRE‐free calculations than for the relativistic ones. SREs yield smaller, flatter, and more positive σ‐holes. Finally, we highlight the importance of diffuse functions in the basis sets and provide quantitative arguments for using basis sets with pseudopotentials as an affordable alternative to a more rigorous Douglas‐Kroll‐Hess relativistic theory.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
International Journal of Quantum Chemistry
ISSN
1097-461X
e-ISSN
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Volume of the periodical
120
Issue of the periodical within the volume
23
Country of publishing house
US - UNITED STATES
Number of pages
12
Pages from-to
"e26392-1"-"e26392-12"
UT code for WoS article
000561182600001
EID of the result in the Scopus database
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