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Computational studies on density function theory for the bimolecular metathesis reaction CH 3 +HCl⇔︁CH 4 +Cl
Author(s) -
Zhou Zhengyu,
Chen Guang,
Zhou Xingmin,
Fu Hui
Publication year - 2001
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.10028
Subject(s) - chemistry , density functional theory , transition state , electron transfer , ab initio , electron localization function , atom (system on chip) , computational chemistry , electron , catalysis , quantum mechanics , physics , organic chemistry , computer science , embedded system
Density function theory has been applied to alkyl radical reaction to get helpful data for its geometric parameters, energy, and vibrational frequency compared with results obtained by ab initio methods and experimental values. The geometry optimization of the transition state, the precursor complex and the successor complex were performed at the 6‐311G* basis set level. The transition state of the CH 4 Cl system of the reaction computed was in agreement with the prediction of Benson. From analysis of the vibration frequency and the net charge on the atom of the precursor complex, transition state, successor complex and the isolated state, the reaction mechanism was derived which we complicated with the bond‐rupture electron‐transfer theory. The atom H in molecule HCl attacks the atom C, forming a transition state via the precursor complex and the electron transfer happens in the precursor complex. The reaction rate of the electron transfer determines the rate of the whole reaction to a certain extent, and active energy, electronic coupling matrix element, and reorganization energy were obtained. © 2001 Wiley Periodicals, Inc. Int J Quantum Chem, 2001