Two-photon absorption property of Cl-substituted diphenylacetylenes by optical-probing photoacoustic spectroscopy

Two-photon absorption spectra and two-photon absorption cross sections of Cl-substituted diphenylacetylenes (ClDPAs) were investigated by optical-probing photoacoustic spectroscopy and quantum chemical calculations for the first time. The two-photon absorption spectra of ClDPAs exhibited intense two-photon absorption bands at around 480 nm, which are forbidden by one-photon absorption. The two-photon absorption cross sections σ⁽²⁾ of o-, m-, and p-ClDPAs at 476 nm were determined to be 22 ± 1, 23 ± 1, and 38 ± 2 GM, respectively. Compared with diphenylacetylene (DPA) (27 GM at 472 nm), the σ⁽²⁾ values of o- and m-ClDPAs were lower, while that of p-ClDPA was higher. Simulated two-photon absorption spectra using the TD-B3LYP/6-311+G(d,p) level of calculations within the Tamm-Dancoff approximation, based on the three-state model, well agreed with the experimental results. The difference in the σ⁽²⁾ values of DPA and ClDPAs was responsible for those in the transition dipole moments between the intermediate and the final states.