Reaction pathways for the triplet methylene abstraction CH/sub 2/(/sup 3/B/sub 1/) + H/sub 2/. -->. CH/sub 3/ + H/sup 1a/

Journal Article · Wed May 01 04:00:00 EDT 1974 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00816a008· OSTI ID:6447947

Baskin, C P ^[1]; Bender, C F; Bauschlicher, Jr, C W; Schaefer, III, H F

---

1. Univ. of California, Berkeley

A nonempirical quantum mechanical study of the reaction of triplet methylene with molecular hydrogen has been carried out. A contracted Gaussian basis set of double zeta quality was employed. Following the determination of each self-consistent-field wave function, configuration interaction was performed including all singly and doubly excited configurations (a total of 649). The potential surface was studied in three dimensions and a total of 780 points computed. From these data several approximations to the minimum energy path have been computed and compared. The reaction exothermicity is computed to be 5.37 kcal/mol, in good agreement with experiment, 4.5 kcal/mol. The predicted barrier height is 15.5 kcal/mol, a result consistent with the lack of any observed reaction between CH/sub 2/(/sup 3/B/sub 1/) and H/sub 2/ at 300/sup 0/K. The predicted barrier is 4.2 kcal/mol less than that obtained by Carr using the bond energy bond order (BEBO) method. The saddle point geometry is predicted to be H-H = 0.90 A, H-C = 1.40 A, and angle HCH = 126.5/sup 0/. 3 figures.

• OSTI ID: 6447947
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 96:9; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BOND ANGLE
BOND LENGTHS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CONFIGURATION INTERACTION
DEPLETION LAYER
DIMENSIONS
ELEMENTS
FUNCTIONS
GAUSS FUNCTION
HYDROGEN
KINETICS
LAYERS
LENGTH
MECHANICS
MEDIUM TEMPERATURE
METHYLENE RADICALS
NONMETALS
PHYSICAL PROPERTIES
QUANTUM MECHANICS
RADICALS
REACTION KINETICS
SELF-CONSISTENT FIELD
TEMPERATURE DEPENDENCE
THERMODYNAMIC PROPERTIES
WAVE FUNCTIONS