SINDO1 STUDY OF PHOTOISOMERIZATION AND PHOTOFRAGMENTATION OF CYCLOPENTANONE.

Article abstract of DOI:10.1021/ja00321a009

The photoisomerization of cyclopentanone to 4-pentenal and the photofragmentation to cyclobutane and carbon monoxide or to two ethylene and carbon monoxide was investigated by the SINDO1 method including configuration interaction (CI). Structures and energies of all pertinent ground and excited states as well as transition states and intermediates were calculated. The mechanism for all reactions involves excitation to S//1 and intersystem crossing to T//1 or T//2. The triplets lead to diradical intermediates from which further reaction to the products takes place. The dependence of product distribution on excitation wavelength is discussed.