Stability of Hartree-Fock solutions and potential-energy surfaces in a reaction involving inversion of the filled and vacant MO of reagent and product. Part 1. Two degenerate reaction channels for the isomerization of CO/sub 2/

Journal Article · Sun Mar 01 04:00:00 EST 1987 · J. Struct. Chem. (Engl. Transl.); (United States)

OSTI ID:5886820

Glukhovtsev, M N; Simkin, B Ya; Minkin, V I

There may be a region in the potential-energy surface (PES) a reaction forbidden by symmetry in the ground electronic state but occurring with inversion of the filled and vacant MO of the reagent and product in which the corresponding solutions obtained in the restricted Hartree-Fock approximation are singlet-unstable. There are then singlet-stable solutions with lower energies, but which correspond to configurations of lower symmetry. As a result, the PES may have reaction channels of reduced symmetry. An example is considered of the cyclization of a linear D/sub infinity h/ structure for CO/sub 2/ to the C/sub 2V/ structure forbidden by symmetry for the ground electronic state. MINDO/3 calculations show that a curve with two wells applies for the region in the PES of the ground singlet state for which the RHF solutions are singlet-unstable, where the section of the minimum-energy path along the distortion coordinate leads to a geometrical configuration of lower symmetry, i.e., there are two degenerate reaction channels in this region of the PES, which correspond to geometrical configurations of symmetry C/sub 1/.

• Research Organization: M. A. Suslov Rostov State Univ., USSR
• OSTI ID: 5886820
• Journal Information: J. Struct. Chem. (Engl. Transl.); (United States), Journal Name: J. Struct. Chem. (Engl. Transl.); (United States) Vol. 27:5; ISSN JSTCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ATOMIC MODELS
BOND LENGTHS
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPUTER CODES
COMPUTERIZED SIMULATION
CONFIGURATION INTERACTION
DIMENSIONS
DIPOLE MOMENTS
ELECTRONIC STRUCTURE
ENERGY
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXCITED STATES
FORBIDDEN TRANSITIONS
GROUND STATES
HARTREE-FOCK METHOD
ISOMERIZATION
KINETICS
LENGTH
M CODES
MATHEMATICAL MODELS
MECHANICS
MOLECULAR MODELS
MOLECULAR ORBITAL METHOD
MOLECULAR STRUCTURE
OXIDES
OXYGEN COMPOUNDS
POTENTIAL ENERGY
QUANTUM MECHANICS
REACTION KINETICS
SIMULATION
STABILITY
SYMMETRY