Abstract
The three‐photon ionization spectrum of liquid benzene is reported in the 360–440 nm one‐photon spectral region. Simultaneous two‐photon absorption indirectly populates what appears to be the lowest singlet excimer state in the first step of the ionization sequence. Absorption of a third photon by the excimer then reaches superexcited states of the liquid. The influence of temperature and applied electric field on the overall ion yield can be rationalized if these superexcited levels collapse into geminate charge pairs of ≊25 A radius. Free charge carriers are finally formed by thermal ionization of geminate pairs with efficiencies on the order of 10−3.
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