ETS-NOCV description of σ-hole bonding

doi:10.1007/s00894-012-1591-0

ETS-NOCV description of σ-hole bonding

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ETS-NOCV description of σ-hole bonding

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punktacja MEiN [2013 A]: 25

title:	ETS-NOCV description of σ-hole bonding
author:	Dyduch Karol , Mitoraj Mariusz , Michalak Artur
journal title:	Journal of Molecular Modeling
volume:	19
issue:	7
date of publication :	2013
pages:	2747-2758
ISSN:	1610-2940
eISSN:	0948-5023
DOI:	10.1007/s00894-012-1591-0
URL:	https://link.springer.com/content/pdf/10.1007%2Fs00894-012-1591-0.pdf
date accessed:	2019-02-07
notes:	Karol Dyduch - Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University
language:	English
journal language:	English
abstract in English:	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.
affiliation:	Wydział Chemii : Zakład Chemii Teoretycznej im. K. Gumińskiego, Wydział Chemii : Zakład Metod Obliczeniowych Chemii
type:	journal article
subtype:	academic paper