Ultrafast excited state absorption and charge separation in phenylene-based conjugated polymers

Ultrafast pump-probe spectroscopy of phenylene-based -conjugated polymers give low and high energy photoinduced absorptions (PAs) to final states with very different relaxation behavior. While the low energy two-photon state that is reached in PA relaxes to the optical exciton in ultrafast times, the higher energy two-photon state violates the Vavilov–Kasha rule and instead of relaxing to the optical exciton undergoes interchain dissociation to a polaron pair state. We have calculated the excited state absorptions of long oligomers of poly-paraphenylene and poly-paraphenylenevinylene within a rigid band correlated electron Hamiltonian, using the complete -electron basis and the powerful multi-reference singles and double configuration interaction technique. Our calculated PA spectra well reproduce the experimental PA. We further show that there exists a fundamental difference in the natures of the wavefunctions of the final states that are reached in low and high energy PA, and the difference originates from the existence of multiple kinds of bands in phenylene-based systems within one-electron theory. We speculate that the violation of the Vavilov–Kasha rule and charge separation into polaron pairs upon excitation to the high energy two-photon state is a consequence of its specific electronic structure, and discuss an earlier work on wavelength dependent photoconductivity of poly-paraphenylenevinylene to support this conjecture. PACS: 78.47.+p; 78.20.Bh; 42.65.Re; 78.40.Me; 78.66.Qn