A THEORETICAL-STUDY OF THE REACTION OF P- POTENTIAL-ENERGY SURFACES AND REACTION DYNAMICS( WITH WATER )

Accurate ab initio computations have been carried out on the minima an d saddle points involved in the dynamics of the reaction of P+ with wa ter using a slightly modified version of G1 and G2 theories (J. Chem. Phys. 94 (1991) 4318). In addition, an approximate classical trajector y method and RRKM theory (Progr. Energy Combust. Sci. 18 (1999) 75) ha ve been employed to study the dynamics of such a reaction. The results indicate that intersystem crossing must take place giving HPOH+((1)A' ), which could be the intermediate responsible for the production of b oth PO+ ((1) Sigma(+)) + H-2(1 Sigma(g)(+)) and POH+ ((2)A') + H(S-2).