ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Using the pump–probe technique with 130 fs laser pulses near 200 nm and near 266 nm the internal conversion of the pyrazine molecule excited to the S2 state has been studied. The lifetime of the S2 state due to internal conversion to the lower electronic states is τIC(2)=(20±10) fs while the lifetime of the secondarily populated S1 state is τIC(1)=(22±1) ps. The results of femtosecond time-resolved electron spectroscopy directly demonstrate the variation of the electron configuration during the internal conversion: The electron spectrum changes significantly on the fs time scale for pyrazine ions produced by ionization via the S2 state with ππ* character and by ionization of S1 state molecules with nπ* configuration after the internal conversion, respectively. The results obtained confirm theoretical estimations of Domcke and co-workers [J. Chem. Phys. 95, 7806 (1991); J. Phys. Chem. 97, 12466 (1993)] who describe the internal conversion in the pyrazine molecule on the basis of a conical intersection of the corresponding potential energy surfaces. © 2000 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.481008
