On the role of charge transfer in halogen bonding

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F17%3A00474255" target="_blank" >RIV/61388963:_____/17:00474255 - isvavai.cz</a>

Result on the web

<a href="http://pubs.rsc.org/en/content/articlehtml/2017/cp/c6cp07475h" target="_blank" >http://pubs.rsc.org/en/content/articlehtml/2017/cp/c6cp07475h</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c6cp07475h" target="_blank" >10.1039/c6cp07475h</a>

Result language

angličtina

Original language name

On the role of charge transfer in halogen bonding

Original language description

The role of charge transfer in halogen bonding is the subject of an ongoing debate and controversy. It is clear from experimental data that charge transfer occurs in halogen bonds, but its contribution to the energetics of the interaction can be evaluated only computationally. Since the charge transfer is not a physically well-defined property, there are multiple computational approaches, which could yield very different results. In this work, we investigate this topic using our recently developed method based on constrained DFT, which allows the quantification of net charge transfer and the associated interaction energy component [Rezac. et al., J. Chem. Theory Comput., 2015]. It is based on the spatial definition of molecular fragments using the superimposed electron density of non-interacting fragments as a reference state free of charge transfer. This definition is close to the intuitive view of charge transfer, yet it removes any arbitrariness in the partitioning of the molecular complex. It has been shown to be very reliable as it avoids the issues encountered in other definitions of charge transfer. For example, the results are independent of the basis set. These calculations are complemented with DFT-SAPT decomposition, which yields the other components of the interaction energy. We have found the energetic contribution of charge transfer to halogen bonding to be rather small, on average about 10% of the interaction energy, which is less than that in hydrogen bonds. Even in very strong halogen bonds, where the absolute value of the charge-transfer energy becomes larger, it is still only a small fraction of the other attractive terms obtained from DFT-SAPT. These results suggest that although it is present, charge transfer is not the determining factor in halogen bonding.

Czech name

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Czech description

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Type

J_imp - 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

Project

<a href="/en/project/GBP208%2F12%2FG016" target="_blank" >GBP208/12/G016: Controlling structure and function of biomolecules at the molecular scale: theory meets experiment</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2017

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

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Volume of the periodical

19

Issue of the periodical within the volume

1

Country of publishing house

GB - UNITED KINGDOM

Number of pages

13

Pages from-to

791-803

UT code for WoS article

000391725300082

EID of the result in the Scopus database

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