The pitzer free rotor model for nondegenerate modes: Application to the long-range behavior of halogen radical reactions with substituted olefins

Journal of Physical Chemistry A

Volumn 107, Issue 22, 2003, Pages 4483-4489

  Kharroubi, Mohamed ^a   De Sainte Claire, Pascal ^a,b  

^a AIX MARSEILLE UNIVERSITY   (France)

^b CNRS   (France)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; ELECTRONIC STRUCTURE; HALOGEN ELEMENTS; OLEFINS; ROTORS;

PITZER MODEL;

RATE CONSTANTS;

EID: 0037497061     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0258614     Document Type: Article

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73. 2. The goal of this calculation was to select appropriate active orbitals in order to reproduce the QCISD(T) C=C bond length of 1.330 Å. Indeed, this bond undergoes key changes during the association reaction with a halogen radical. Including the highest occupied and lowest unoccupied molecular orbitals in the active space, π HOMO and π* LUMO, respectively, resulted in a significantly shorter C=C bond length (1.315 A) with respect to QCISD(T) results. Including the C=C σ and σ* MOs in the active space resulted in much better agreement (1.331 A). Thus a CAS(4,4) calculation (i.e., four electrons in four molecular orbitals: a, π, σ*, and π*) was needed to get reliable energies for the reactant molecule. In the associated species, two of the valence p orbitals of the incoming halogen radical have the correct symmetry (those in the yz plane, see Figure 2). These should be included in the active space, thus resulting in four more orbitals and three extra electrons. Consequently, a CAS(7,8) calculation was the minimum level required to obtain an accurate potential energy surface. Such calculations, however, are beyond the scope of this work.
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