ETS-NOCV description of σ-hole bonding

2013
journal article
article
40
dc.abstract.enThe ETS-NOCVanalysis was applied to describe the σ -hole in a systematic way in a series of halogen com- pounds, CF 3 -X ( X 0 I, Br, Cl, F), CH 3 I, and C(CH3) n H 3-n -I ( n 0 1,2,3), as well as for the example germanium-based systems. GeXH 3 , X 0 F,Cl,H.Further,theETS-NOCV analysis was used to characterize bonding with ammonia for these systems. The results show that the dominating contribution to the deformation density, Δ ρ 1 , exhibits the negative-value area with a minimum, corresponding to σ - hole. The “ size ” (spatial extension of negative value) and “ depth ” (minium value) of the σ -hole varies for different X in CF 3 -X, and is influenced by the carbon substituents (fluorine atoms, hydrogen atoms, methyl groups). The size and depth of σ -hole decreases in the order: I, Br, Cl, F in CF 3 -X. In CH 3 -I and C(CH3) n H 3-n -I, compared to CF 3 -I, introduction of hydrogen atoms and their subsequent replacements by methyl groups lead to the systematic de- crease in the σ -hole size and depth. The ETS-NOCV σ -hole picture is consistent with the existence the positive MEP area at the extension of σ -hole generating bond. Finally, the NOCV deformation density contours as well as by the ETS orbital-interaction e nergy indicate that the σ -hole-based bond with ammonia contains a degree of covalent contribu- tion. In all analyzed systems, it was found that the electro- static energy is approximately two times larger than the orbital-interaction term, confirming the indisputable role of the electrostatic stabilization in halogen bonding and σ -hole bonding.pl
dc.affiliationWydział Chemii : Zakład Chemii Teoretycznej im. K. Gumińskiegopl
dc.affiliationWydział Chemii : Zakład Metod Obliczeniowych Chemiipl
dc.contributor.authorDyduch, Karol - 107712 pl
dc.contributor.authorMitoraj, Mariusz - 160142 pl
dc.contributor.authorMichalak, Artur - 101384 pl
dc.date.accession2019-02-07pl
dc.date.accessioned2015-06-23T11:09:42Z
dc.date.available2015-06-23T11:09:42Z
dc.date.issued2013pl
dc.date.openaccess0
dc.description.accesstimew momencie opublikowania
dc.description.additionalKarol Dyduch - Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian Universitypl
dc.description.number7pl
dc.description.physical2747-2758pl
dc.description.versionostateczna wersja wydawcy
dc.description.volume19pl
dc.identifier.doi10.1007/s00894-012-1591-0pl
dc.identifier.eissn0948-5023pl
dc.identifier.issn1610-2940pl
dc.identifier.projectROD UJ / Ppl
dc.identifier.urihttp://ruj.uj.edu.pl/xmlui/handle/item/10112
dc.identifier.weblinkhttps://link.springer.com/content/pdf/10.1007%2Fs00894-012-1591-0.pdfpl
dc.languageengpl
dc.language.containerengpl
dc.rightsUdzielam licencji. Uznanie autorstwa 4.0 Międzynarodowa*
dc.rights.licenceCC-BY
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/legalcode.pl*
dc.share.typeinne
dc.subtypeArticlepl
dc.titleETS-NOCV description of σ-hole bondingpl
dc.title.journalJournal of Molecular Modelingpl
dc.typeJournalArticlepl
dspace.entity.typePublication
dc.abstract.enpl
The ETS-NOCVanalysis was applied to describe the σ -hole in a systematic way in a series of halogen com- pounds, CF 3 -X ( X 0 I, Br, Cl, F), CH 3 I, and C(CH3) n H 3-n -I ( n 0 1,2,3), as well as for the example germanium-based systems. GeXH 3 , X 0 F,Cl,H.Further,theETS-NOCV analysis was used to characterize bonding with ammonia for these systems. The results show that the dominating contribution to the deformation density, Δ ρ 1 , exhibits the negative-value area with a minimum, corresponding to σ - hole. The “ size ” (spatial extension of negative value) and “ depth ” (minium value) of the σ -hole varies for different X in CF 3 -X, and is influenced by the carbon substituents (fluorine atoms, hydrogen atoms, methyl groups). The size and depth of σ -hole decreases in the order: I, Br, Cl, F in CF 3 -X. In CH 3 -I and C(CH3) n H 3-n -I, compared to CF 3 -I, introduction of hydrogen atoms and their subsequent replacements by methyl groups lead to the systematic de- crease in the σ -hole size and depth. The ETS-NOCV σ -hole picture is consistent with the existence the positive MEP area at the extension of σ -hole generating bond. Finally, the NOCV deformation density contours as well as by the ETS orbital-interaction e nergy indicate that the σ -hole-based bond with ammonia contains a degree of covalent contribu- tion. In all analyzed systems, it was found that the electro- static energy is approximately two times larger than the orbital-interaction term, confirming the indisputable role of the electrostatic stabilization in halogen bonding and σ -hole bonding.
dc.affiliationpl
Wydział Chemii : Zakład Chemii Teoretycznej im. K. Gumińskiego
dc.affiliationpl
Wydział Chemii : Zakład Metod Obliczeniowych Chemii
dc.contributor.authorpl
Dyduch, Karol - 107712
dc.contributor.authorpl
Mitoraj, Mariusz - 160142
dc.contributor.authorpl
Michalak, Artur - 101384
dc.date.accessionpl
2019-02-07
dc.date.accessioned
2015-06-23T11:09:42Z
dc.date.available
2015-06-23T11:09:42Z
dc.date.issuedpl
2013
dc.date.openaccess
0
dc.description.accesstime
w momencie opublikowania
dc.description.additionalpl
Karol Dyduch - Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University
dc.description.numberpl
7
dc.description.physicalpl
2747-2758
dc.description.version
ostateczna wersja wydawcy
dc.description.volumepl
19
dc.identifier.doipl
10.1007/s00894-012-1591-0
dc.identifier.eissnpl
0948-5023
dc.identifier.issnpl
1610-2940
dc.identifier.projectpl
ROD UJ / P
dc.identifier.uri
http://ruj.uj.edu.pl/xmlui/handle/item/10112
dc.identifier.weblinkpl
https://link.springer.com/content/pdf/10.1007%2Fs00894-012-1591-0.pdf
dc.languagepl
eng
dc.language.containerpl
eng
dc.rights*
Udzielam licencji. Uznanie autorstwa 4.0 Międzynarodowa
dc.rights.licence
CC-BY
dc.rights.uri*
http://creativecommons.org/licenses/by/4.0/legalcode.pl
dc.share.type
inne
dc.subtypepl
Article
dc.titlepl
ETS-NOCV description of σ-hole bonding
dc.title.journalpl
Journal of Molecular Modeling
dc.typepl
JournalArticle
dspace.entity.type
Publication
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