Ab initio studies for the photodissociation mechanism of hydroxyacetone.
The reaction pathways for CH(3)COCH(2)OH (hydroxyacetone) photodissociation on the low-lying electronic states have been studied with use of the CASSCF energy gradient techniques. The S(0)/S(1) and S(1)/T(1) intersection points were determined by the state-average CASSCF method. Two main reaction pathways, which are possible to the photodissociation, have been studied. It has been found that the mechanism is stepwise, and belongs to Norrish type-I reaction. The n --> pi* excitation leads to the first excited singlet state, followed by the intersystem crossing from S(1) to T(1). On the T(1) potential energy surface, the system can dissociate adiabatically to CH(3)(x) +COCH(2)OH( x) and CH(3)CO(x)+CH(2)OH(x). The COCH(2)OH(x) and CH(3)CO(x) radicals can further dissociate into CO, OH, and other fragments. Our calculated results are in good agreement with recent experimental results.
Wu
Yong
Y
Institute of Theoretical and Computational Chemistry, Department of Chemistry, Nanjing University, Nanjing 210093, People's Republic of China.
Xie
Daiqian
D
Xue
Ying
Y