J. Thogersen et al., FEMTOSECOND PHOTOLYSIS OF CLO2 IN AQUEOUS-SOLUTION, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 101(18), 1997, pp. 3317-3323
The photolysis of aqueous ClO2 has been studied with a new femtosecond
transient absorption spectrometer, allowing absorbance changes as sma
ll as Delta A approximate to 1 x 10(-4) to be recorded with a time res
olution of 150 fs. ClO2 was photolyzed at 390 nm and the ultrafast for
mation and decay of photoproducts were monitored at 260, 390, and 780
nm. As expected from earlier studies, Cl atoms are formed with a quant
um yield of Phi(Cl) = 0.1. However, the rate of formation is nearly 2
orders of magnitude higher than that reported. Moreover, Cl is the onl
y photoproduct that survives 25 ps after the photolysis pulse. The mai
n photolytic products, ClO + O, formed with a quantum yield of 0.9, di
sappear through fast germinate recombination, producing vibrational ex
cited ClO2 in the electronic ground state. The vibrational relaxation
of this species occurs with a time constant of 10 ps. The vanishing yi
eld of cage escape for ClO + O, which contrasts with the reported resu
lt of the photolysis at 355 nm, indicates that the amount of excess en
ergy imparted to these products at 390 nm is insufficient to enable th
em to separate. The decay of a photoinduced dichroism observed at 390
nm is interpreted as an orientational relaxation of ground-state ClO2,
the time constant (0.6 ps) agreeing with that calculated from the hyd
rodynamical slip model.