Theoretical studies of the photochemical dynamics of acetylacetone: isomerzation, dissociation, and dehydration reactions

J Phys Chem A. 2006 Apr 6;110(13):4434-41. doi: 10.1021/jp057306i.


The potential energy surfaces of the C-O cleavage, rotational isomerization, keto-enolic tautomerization, and dehydration reactions of acetylacetone in the lowest triplet and ground states have been determined using the complete active space self-consistent field and density functional theory methods. The main photochemical mechanism obtained indicates that the acetylacetone molecule in the S(2)((1)pipi*) state can relax to the T(1)((3)pipi*) state via the S(2)-S(1) vibronic interaction and an S(1)/T(1)/T(2) intersection. The C-O fission pathway is the predominant dissociation process in the T(1)((3)pipi) state. Rotational isomerization reactions proceed difficultly in the ground state but very easily in the T(1)((3)pipi*) state. Keto-enolic tautomerization takes place with little probability for acetylacetone in the gas phase.