PHOTOFRAGMENTATION OF OCLO((A)OVER-TILDE(2)A(2) NU(1)NU(2)NU(3))-]CL(2P(J))-2(O)

The photodissociation dynamics of OClO((2)A(2) nu(1)nu(2)nu(3)) --> Cl (P-2(J)) + O-2 is investigated in the wavelength region between 360 an d 450 nm. Observation of nascent chlorine atom fragments produced in t heir electronic ground state is performed by means of three-photon exc itation with subsequent recording of the vacuum ultraviolet laser-indu ced fluorescence. Mode-specific branching ratios between the dominant ClO(X(2)Pi(Omega)) + O(P-3(J)) and the minor Cl(P-2(J)) + O-2 channel are obtained. The observed quantum yield for Cl production is determin ed to be below 3.6% at photolysis wavelengths between 365 and 450 nm d epending on the respective vibrational level of OClO((2)A(2)nu(1)nu(2) nu(3)). At dissociation wavelengths below 365 nm, a sharp rise in the chlorine formation is observed resulting from a secondary photolysis s tep where vibrationally excited ClO(X(2)Pi(Omega), nu greater than or equal to 4) radicals are dissociated.