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Molecular structure of acrolein electronic states

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00439a012· OSTI ID:7332452

The ground and low-lying singlet and triplet states of acrolein, CH/sub 2/CHCHO, have been studied with ab initio SCF methods using a double zeta basis set of Gaussian orbitals. The cis and trans ground-state geometries were optimized and vertical excitation energies were determined for n ..-->.. ..pi..* and ..pi.. ..-->.. ..pi..* singlet and triplet states. The separation between the cis and trans ground states was found to be 540 cm/sup -1/. Optimization of major bond lengths placed the ..pi.. ..-->.. ..pi..* states very close energetically to the n ..-->.. ..pi..* states. For all excited states, the carbon--oxygen bond length was substantially longer than in the ground state. For the ..pi.. ..-->.. ..pi..* singlet and triplet, the single/double bond character of the carbon--carbon bonds is interchanged with respect to the ground state. The ground and lowest excited singlet and triplet states are planar.

Research Organization:
Univ. of California, Berkeley
OSTI ID:
7332452
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 98:23; ISSN JACSA
Country of Publication:
United States
Language:
English