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Ab initio study of the formation of C 3 H 3 + from the reaction of CH 3 + with acetylene
Author(s) -
López Ramón,
Sordo José A.,
Sordo Tomás L.,
von Ragué Schleyer Paul
Publication year - 1996
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(199605)17:7<905::aid-jcc13>3.0.co;2-9
Subject(s) - acetylene , ab initio , chemistry , metastability , computational chemistry , fragmentation (computing) , atomic physics , transition state , physics , biochemistry , organic chemistry , computer science , catalysis , operating system
Ab initio molecular orbital theory has been used to study the mechanism ofthe formation of C 3 H 3 + from the reaction ofCH 3 + with acetylene. The highest level geometry optimizations andfrequencies were computed at MP2‐FC/6‐31G**; single point energies of all the criticalstructures were computed to the MP4‐FC/6‐31G**//MP2‐FC/6‐31G** theory level. One ofthe three alternative transition structures leading to the formation ofC 3 H 3 + gives the cyclopropenyl cation and the other twothe propargyl cation. The proportions of C 3 H 2 D + andC 3 HD 2 + obtained when CD 3 + reactswith acetylene, and the composite nature of the metastable peak observed for the[C 3 H 5 ] + →[C 3 H 3 ] + + H 2 fragmentation are explained by assuming a different degree of deuteriumscrambling depending on the energy of the system. © 1996 by John Wiley &Sons, Inc.