Computational study of carbon atom (3P and 1D) reaction with CH2O. Theoretical evaluation of 1B1 methylene production by C (1D).
Singlet and triplet free energy surfaces for the reactions of C atom ((3)P and (1)D) with CH(2)O are studied computationally to evaluate the excited singlet ((1)B(1)) methylene formation from deoxygenation of CH(2)O by C ((1)D) atom as suggested by Shevlin et al. Carbon atoms can react by addition to the oxygen lone pair or to the C=O double bond on both the triplet and singlet surfaces. Triplet C ((3)P) atoms will deoxygenate to give CO plus CH(2) ((3)B(1)) as the major products, while singlet C ((1)D) reactions will form ketene and CO plus CH(2) ((1)A(1)). No definitive evidence of the formation of excited singlet ((1)B(1)) methylene was found on the singlet free energy surface. A conical intersection between the (1)A' and (1)A' ' surfaces located near an exit channel may play a role in product formation. The suggested (1)B(1) state of methylene may form via the (1)A' ' surface only if dynamic effects are important. In an effort to interpret experimental observation of products trapped by (Z)-2-butene, formation of cis- and trans-1,2-dimethylcyclopropane is studied computationally. The results suggests that "hot" ketene may react with (Z)-2-butene nonstereospecifically.
Joo
Hyun
H
Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849, USA.
Shevlin
Philip B
PB
McKee
Michael L
ML