Hn. Ghosh et al., PICOSECOND FLASH-PHOTOLYSIS STUDIES ON PHENOTHIAZINE IN ORGANIC AND MICELLAR SOLUTION, JOURNAL OF PHYSICAL CHEMISTRY B, 101(13), 1997, pp. 2315-2320
Picosecond laser flash photolysis studies are carried out on phenothia
zine (PTH) in cyclohexane, alcoholic solvents such as methanol and dec
anol, and aqueous micellar solutions like Triton X-100, Brij-58, and s
odium dodecyl sulfate (SDS) on excitation at different wavelengths, vi
z., 266 and 355 nm. In cyclohexane solution, S-1 --> S-n transient abs
orption has been characterized and the intersystem crossing process ha
s been studied. In alcoholic and micellar media, transient absorptions
due to PTH cation radical and solvated electron (e(s)(-)) have also b
een observed along with the absorption of singlet and triplet states o
f PTH. Quantum yields of the different transient species in different
solvents have been determined using both 266 and 355 nm excitation. De
pendence of the yields of photoionization and singlet excited state on
light intensity has also been investigated at these two excitation wa
velengths. It is observed that the photoionization of PTH in methanol
at 355 nm is a stepwise biphotoionic process. In aqueous SDS micellar
medium, the photoionization is found to be monophotonic at 266 nm, but
both mono- and biphotonic processes seem to operate at 355 nM. Direct
evidence of the involvement of the S-1 state of PTH in the biphotonic
processes is presented.