The unimolecular triple dissociation of glyoxal: Transition-state structures optimized by configuration interaction and coupled cluster methods

Journal Article · Mon Nov 27 04:00:00 EST 1989 · Journal of the American Chemical Society; (USA)

DOI:https://doi.org/10.1021/ja00202a016· OSTI ID:7068630

Scuseria, G E; Schaefer, III, H F ^[1]

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1. Univ. of Georgia, Athens (USA)

Several high-level ab initio theoretical methods have been used to investigate the proposed (1980) triple whammy mechanism for the unimolecular dissociation of glyoxal. Basis sets of double zeta plus polarization (DZ + P) and triple zeta plus double polarization (TZ + 2P) quality have been used in connection with CISD, CCSD, and CCSDT-1 theoretical methods. The theoretical studies show unambiguously that the triple dissociation mechanism is operative under conditions used in the laboratory to investigate glyoxal photochemistry. Also confirmed, contrary to existing experiments, is the early (1975) theoretical prediction of Dykstra that the C-C single bond distance of cis-glyoxal is longer than for trans-glyoxal. Vibrational frequencies for both cis- and trans-glyoxal are predicted and show good qualitative agreement with existing experimental data.

• OSTI ID: 7068630
• Journal Information: Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 111:20; ISSN 0002-7863; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400200 -- Inorganic
Organic
& Physical Chemistry
400500* -- Photochemistry
ALDEHYDES
CALCULATION METHODS
CHEMISTRY
CLUSTER MODEL
DATA ANALYSIS
DISSOCIATION
GLYOXAL
MATHEMATICAL MODELS
NUCLEAR MODELS
ORGANIC COMPOUNDS
PHOTOCHEMISTRY