SN2 reactions as two-state problems: diabatic MO-CI calculations on lithium (Li3-, Li2H-) and chlorine (Cl3-, ClCH3Cl-)

Autor:	Jean-Paul Malrieu, G. Sini, O. K. Kabbaj, M. B. Lepetit, P. C. Hiberty
Rok vydání:	1991
Předmět:	Chemistry Ab initio Diabatic chemistry.chemical_element Walsh diagram General Chemistry Biochemistry Diatomic molecule Catalysis Colloid and Surface Chemistry Computational chemistry Nucleophilic substitution SN2 reaction Physical chemistry Lithium Adiabatic process
Zdroj:	Journal of the American Chemical Society. 113:5619-5627
ISSN:	1520-5126 0002-7863
DOI:	10.1021/ja00015a015
Popis:	A diabatic interpretation of S N 2 reactions A − +BC→AB+C − has been recently proposed by Shaik and Pross, which relates the barrier heights to the electroaffinities of A and BC reactant systems. This model rests on qualitative VB correlation diagrams. The present work proposes a similar diabatic picture of these reactions, based on ab initio MO-CI calculations in extended basis sets. The two lowest adiabatic 1 Σ + states are rotated to generate nearly diabatic states, providing nearly diabatic potential surfaces correlating A − +BC and AB − +C for one of them, A+BC − and AB+C − for the other, and an effective coupling between them. The procedure is applied to two symmetrical reactions (Li 3 − and Cl 3 − ) and one nonsymmetrical reaction (Li 2 H − ) and may be easily fitted by LEPS-type interpolations, irrespective of the stability of the transition complex
Databáze:	OpenAIRE
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