Description of chemical reactions by the method of the Full Optimized Reaction Space. The ring-opening of unsubstituted and substituted cyclopropylidene to allene
The ring-opening reaction of singlet cyclopropylidene to singlet D/sub 2d/ allene is studied by means of ab-initio FORS-MCSCF calculations. The energy surface is determined for many intermediate geometries defined by the C-C-C opening angle and the two CH/sub 2/ rotation angles. For each choice of these three variables, the remaining twelve internal coordinates are relaxed by energy minimization. The results obtained differ markedly from those of earlier, less sophisticated calculations. Since experimental evidence, based exclusively on the substituted species, suggests that the reaction is stereospecific, a potential simulating the steric effects of substituents is added to the originally calculated surface. The results are analyzed and it is shown that all experimental observations can be adequately explained solely by means of nonbonded interactions between substituent groups. 92 refs., 27 figs., 20 tabs.
- Research Organization:
- Ames Lab., IA (USA)
- DOE Contract Number:
- W-7405-ENG-82
- OSTI ID:
- 5370831
- Report Number(s):
- IS-T-1212; ON: DE85015562
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKANES
ALLENE
CHEMICAL REACTIONS
CYCLOALKANES
DIENES
ENERGY-LEVEL TRANSITIONS
HYDROCARBONS
ISOMERIC TRANSITIONS
ISOMERIZATION
ISOMERS
MATHEMATICAL MODELS
MOLECULAR STRUCTURE
OPTICAL ACTIVITY
ORGANIC COMPOUNDS
POLYENES
STEREOCHEMISTRY