Ab initio calculations of potential energy surface for reaction of nucleophilic addition of H/sup -/ ion to methylacetylene (in Russian)
Within the framework of the Hartree-Fock-Roothaan Method, using double-xi basis sets 3-21++G and (6-31++G//3-21++G), the minimum energy paths (MEPs) have been calculated for reactions of nucleophilic addition of the hydride ion H/sup -/ to the methylacetylene molecule: CH/sub 3/-C triple bond CH + H/sup -/ ..-->.. (CH/sub 3/-CH=CH)/sup -/ (1) CH/sub 3/-C triple bond CH + H/sup -/ ..-->.. (CH/sub 3/-C=CH/sub 2/)/sup -/ (2). It has been established that the activation energy for reaction (2) is 7.02 kJ/mole lower than for reaction (1). An analysis has been made of the character of electron density distribution along the MEP of each reaction. It has been shown that distortion of geometry of the reactants plays an important role in intensifying the interaction of the frontier orbitals. The reasons for nonfulfillment of Markownikoff's rule for these reactions have been determined. The results from the calculations are compared with calculations reported in the literature for the related reaction of nucleophilic addition of the hydride ion H/sup -/ to the acetylene molecule: HC triple bond CH + H/sup -/ ..cap alpha.. (CH/sub 2/=CH)/sup -/.
- Research Organization:
- M. V. Lomonosov Moscow Institute of Fine-Chemical Technology, USSR
- OSTI ID:
- 6387223
- Journal Information:
- Theor. Exp. Chem. (Engl. Transl.); (United States), Journal Name: Theor. Exp. Chem. (Engl. Transl.); (United States) Vol. 21:3; ISSN TEXCA
- Country of Publication:
- United States
- Language:
- Russian
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Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ACTIVATION ENERGY
ALKYNES
ATOMIC MODELS
BINDING ENERGY
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPUTER CODES
COMPUTERIZED SIMULATION
CONFIGURATION INTERACTION
EFFECTIVE CHARGE
ELECTRON DENSITY
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
ENERGY
ENTHALPY
FUNCTIONS
G CODES
GAUSS FUNCTION
HARTREE-FOCK METHOD
HYDRIDATION
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROGEN TRANSFER
KINETICS
MATHEMATICAL MODELS
MECHANICS
MOLECULES
ORGANIC COMPOUNDS
PERTURBATION THEORY
PHYSICAL PROPERTIES
POLYATOMIC MOLECULES
POTENTIAL ENERGY
PROPYNE
QUANTUM MECHANICS
REACTION HEAT
REACTION KINETICS
SIMULATION
THERMODYNAMIC PROPERTIES