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Reaction ergodography for the additions of HLi and its dimer to acetylene
Author(s) -
Zhao ChengDa,
Chen Bin,
Huang JingAn
Publication year - 1989
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.560360103
Subject(s) - chemistry , acetylene , dimer , molecular orbital , ab initio , computational chemistry , transition state , basis set , molecular orbital theory , molecule , density functional theory , catalysis , organic chemistry
The ab initio calculation has been performed with the addition pathways of HLi and its dimer to acetylene at the RHF/3‐21G basis set. It shows that the reaction mechanisms of these two reactions are rather similar. In either of two reaction pathways, there is a meta‐stable molecular complex near the isolated reactant state. This kind of addition can be treated approximately as the unimolecular reaction in which the molecular complex rearranges into the product. We have estimated the activation entropies and the statistical A factors of these two reactions by the use of RRKM theory. Frontier molecular orbital analysis of these two transition states reveals their HOMOS to be formed from both HOMO‐LUMO and HOMO‐HOMO interactions.