MONOPHOTONIC IONIZATION FROM THE VIBRATIONALLY UNRELAXED EXCITED SINGLET-STATE OF N,N,N',N'-TETRAMETHYL-P-PHENYLENEDIAMINE IN ACETONITRILE SOLUTION

The excitation wavelength dependence of the photoionization yield of N,N,N′,N′-tetramethyl-p-phenylenediamine in acetonitrile has been investigated by using tunable picosecond dye laser photolysis measurements. The monophotonic ionization from the vibrationally unrelaxed state has been observed, the yield of which increased with increasing excitation energy in the S1 state and decreased slightly around the onset of the S2 state. This suggests that the rate of the electron photoejection depends not only on the excess energy contained but also on the excited vibrational mode. © 1990 American Chemical Society.