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A Theoretical Reexamination of the π‐Bond Strengths within the SiH 2 ═ XH n System
Author(s) -
Chen JunXian,
Liu Dong,
Zhang Chang,
Li Jun,
Zhang Hui,
Kim Chan Kyung
Publication year - 2015
Publication title -
bulletin of the korean chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.237
H-Index - 59
ISSN - 1229-5949
DOI - 10.1002/bkcs.10030
Subject(s) - electronegativity , bond dissociation energy , chemistry , covalent bond , bond energy , dissociation (chemistry) , bond length , divalent , thermodynamics , work (physics) , computational chemistry , atomic physics , crystallography , physics , molecule , crystal structure , organic chemistry
In this work, we present a calculation of the π‐bond energy in the SiH 2 ═ XH n system at the QCISD (T)/6‐311++G(3df,2p) level combined with an isogyric correction, which shows that PSub‐DSSE (partly substituted divalent state stabilization energy) is a reliable methodology for analyzing the properties of doubly bonded species by separating the dissociation and substitution effects on either side of the double bonds. Compared to the π‐bond energies in the CH 2 ═ XH n system, those in the SiH 2 ═ XH n system have a better linear relationship with the electronegativity of the element X because of the improvement of the correlation coefficient from 0.802 for the former to 0.924 for the latter. This means that there must be another important factor that comes into effect in the CH 2 ═ XH n system. Through statistical analysis, the covalence difference between Si and X or C and X was finally selected as a second descriptor to explain the magnitude of the π‐bond energies.