✦ LIBER ✦
Microcanonical variational theory of radical recombination by inversion of interpolated partition function. Isotope effect in CH3 + H/D
✍ Scribed by Wendell Forst
- Publisher
- Elsevier Science
- Year
- 1992
- Tongue
- English
- Weight
- 503 KB
- Volume
- 194
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
Application of the title theory to the recombinations CHs+H and CHr+ D leads to the value of o 2 for the isotope effect. Analysis of this result shows that the increase over the value 2"' expected from simple transition state theory comes almost entirely from the ratio of rotational constants of the doubly degenerate rotation of the symmetric-top CH+..X (X=H/D) transition state which represents X moving away from CHa. However the calculated isotope effect remains below the experimental value of z 2.7. Possible reasons for the discrepancy are discussed.