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An ab initio theoretical approach to the gas phase decomposition of C 3 H 7 + produced in ground state Li + + i ‐C 3 H 7 Cl collisions
Author(s) -
Lucas Jose Maria,
de Andrés Jaime,
Albertí Margarita,
Bofill Josep Maria,
AguilarNavarro Antonio
Publication year - 2011
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.22668
Subject(s) - isomerization , chemistry , ground state , ab initio , potential energy surface , decomposition , ion , hydrogen , transition state , atomic physics , computational chemistry , physics , biochemistry , organic chemistry , catalysis
A theoretical study of the potential energy surface (PES) for the decomposition of the i ‐C 3 H 7 +cation has been done at RHF/MP2 level. In a previous study on the Li + + i ‐C 3 H 7 Cl system under single collision conditions, the authors measured the cross section energy dependence for the formation of this cation and its decomposition in C 2 H 3 ++ CH 4 . Theoretical calculations on the PES of the C 3 H 7 +system have provided reaction paths for both, its decomposition channel and its isomerization to n ‐C 3 H 7 + . The former reaction path involves a large increase of one CC bond length of the initial ion, nearly forming a CH 3 neutral fragment that, by interacting with the remaining fragment, abstracts a hydrogen atom, giving methane and C 2 H 3 +as final products. The energy requirement for this reaction is given by the process endoergicity, without any additional potential barrier. For the isomerization reaction, a transition state has been located between both potential wells, with the corresponding reaction path fully characterized by the IRC method. The main features of the calculated PES allow us to interpret, at least qualitatively, the experimental data previously obtained in our group. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011