Excited states of acrolein: abinitio model studies on α,β-unsaturated carbonyl compounds

Abstract

As an explanation of the stereochemistry of photoaddition between α,β-unsaturated carbonyl compounds and olefins, Wiesner suggested that the excited state of the α,β-unsaturated carbonyl compound is pyramidal at the β-carbon. It is shown by abinitio SCF and CI studies that for acrolein in the 1nπ*, 3nπ*, and 3ππ* excited states the β-carbon remains planar. In addition, vertical excitation energies for the 1nπ* and 1ππ*, and adiabatic excitation energies for the 1nπ* and 3nπ* states of trans-acrolein have been calculated.