Abstract
Generation of charge pairs in a ladder-type poly(para-phenylene) was investigated by means of electric field modulated femtosecond pump-probe absorption spectroscopy upon excitation at 3.1 and $4.66\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$. Exciting at $3.1\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$ in the optical ${S}_{0}\ensuremath{\rightarrow}{S}_{1}$ transition, the number of geminately bound electron--hole pairs rises smoothly within the entire exciton life time. Upon excitation at $4.66\phantom{\rule{0.3em}{0ex}}\mathrm{eV}$ an instantaneous generation of geminate pairs superimposed on the more gradual increase is observed. Both processes are field-assisted, albeit differently. The former is attributed to ultrafast dissociation of a hot Franck-Condon state, while the latter is assigned to dissociation of vibrationally relaxed singlet excitons.
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