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Ab initio study of C4H3 potential energy surface and reaction of ground-state carbon atom with propargyl radical

✍ Scribed by Trung Ngoc Le; Alexander M. Mebel; Ralf I. Kaiser

Publisher
John Wiley and Sons
Year
2001
Tongue
English
Weight
579 KB
Volume
22
Category
Article
ISSN
0192-8651

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✦ Synopsis

Abstract

The potential energy surface for the reaction of the ground‐state carbon atom [C(^3^P~j~)] with the propargyl radical [HCCCH~2~(X^2^B~1~)] is investigated using the G2M(RCC,MP2) method. Numerous local minima and transition states for various isomerization and dissociation pathways of doublet C~4~H~3~ are studied. The results show that C(^3^P~j~) attacks the π system of the propargyl radical at the acetylenic carbon atom and yields the n‐C~4~H~3~(^2^A′) isomer i3 after an 1,2‐H atom shift. This intermediate either splits a hydrogen atom and produces singlet diacetylene, [HCCCCH (p1)+H] or undergoes (to a minor amount) a 1,2‐H migration to i‐C~4~H~3~(^2^A′) i5, which in turn dissociates to p1 plus an H atom. Alternatively, atomic carbon adds to the triple CC bond of the propargyl radical to form a three‐member ring C~4~H~3~ isomer i1, which ring opens to i3. Diacetylene is concluded to be a nearly exclusive product of the C(^3^P~j~)+HCCCH~2~ reaction. At the internal energy of 10.0 kcal/mol above the reactant level, Rice–Ramsperger–Kassel–Marcus calculations show about 91.7% of HCCCCH comes from fragmentation of i3 and 8.3% from i5. The other possible minor channels are identified as HCCCC+H~2~ and C~2~H+HCCH. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1522–1535, 2001

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