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Geometric and electronic structures of silicon fluorides SiF n ( n − 4 ) − ( N = 4 – 6) and potential energy surfaces for dissociation reactions SiF 5 − → SiF 4 + F – and SiF 6 2 − → SiF 5 − + F –
Author(s) -
Koval Vitaliy V.,
Minyaev Ruslan M.,
Minkin Vladimir I.
Publication year - 2016
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25184
Subject(s) - chemistry , bond dissociation energy , dissociation (chemistry) , density functional theory , natural bond orbital , basis set , coupled cluster , computational chemistry , silicon , potential energy surface , atomic physics , ion , electronic structure , molecule , physics , organic chemistry
The geometric and electronic structures of a series of silicon fluoridesSiF n ( n − 4 ) −( n = 4 − 6) were computationally studied with the aid of density functional theory (DFT) method with B3LYP and M06‐2X functionals and coupled cluster (CCSD and CCSD(T)) methods with 6‐311++G(d,p) basis set. The nature of the Si‐F bonds in these compounds was analyzed in the framework of the natural bond orbital theory and natural resonance theory. Energy characteristics (heats of reactions and energy barriers) of the dissociation reactionsSiF 5 −→ SiF 4 + F – andSiF 6 2 −→SiF 5 − + F – were calculated using the DFT and CCSD methods. The potential energy surface of elimination of a fluoride anion fromSiF 6 2 −has a specific topology with valley‐ridge inflection points corresponding to bifurcations of the minimal energy reaction path. © 2016 Wiley Periodicals, Inc.