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/
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), Vol. 27:5; Other Information: Translated from Zh. Strukt. Khim.; 27: No. 5, 3-12(Sep-Oct 1986)
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
CARBON DIOXIDE
ATOMIC MODELS
EXCITATION
FORBIDDEN TRANSITIONS
HARTREE-FOCK METHOD
ISOMERIZATION
MOLECULAR MODELS
BOND LENGTHS
CHEMICAL REACTION KINETICS
COMPUTERIZED SIMULATION
CONFIGURATION INTERACTION
DIPOLE MOMENTS
ELECTRONIC STRUCTURE
EXCITED STATES
GROUND STATES
M CODES
MOLECULAR ORBITAL METHOD
MOLECULAR STRUCTURE
POTENTIAL ENERGY
QUANTUM MECHANICS
STABILITY
SYMMETRY
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
COMPUTER CODES
DIMENSIONS
ENERGY
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
KINETICS
LENGTH
MATHEMATICAL MODELS
MECHANICS
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
SIMULATION
400201* - Chemical & Physicochemical Properties
640302 - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory