Journal of Physical Chemistry A, Vol.102, No.39, 7680-7685, 1998
Photofragmentation of OClO((A)over-tilde(2)A(2) nu(1)nu(2)nu(3))-> Cl(2P(J))+O-2
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 and 450 nm. Observation of nascent chlorine atom fragments produced in their electronic ground state is performed by means of three-photon excitation with subsequent recording of the vacuum ultraviolet laser-induced 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 determined to be below 3.6% at photolysis wavelengths between 365 and 450 nm depending 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 step where vibrationally excited ClO(X(2)Pi(Omega), nu greater than or equal to 4) radicals are dissociated.
Keywords:ENHANCED MULTIPHOTON IONIZATION, ABSORPTION CROSS-SECTIONS;PHOTODISSOCIATION DYNAMICS, CHLORINE DIOXIDE, OCLOPHOTODISSOCIATION, STRATOSPHERIC OZONE, ANTARCTIC OZONE, 370NM, CLO, KINETICS