Picosecond investigations of optical limiting mechanisms in King's complex

Abstract

We have investigated the nonlinear optical mechanisms responsible for optical limiting of both picosecond and nanosecond 532-nm optical pulses in the organometallic compound cyclopentadienyliron carbonyl tetramer (King's complex). For fluences below ~200 mJ/cm², picosecond pump-probe measurements in solutions of the King's complex reveal a prompt reverse saturable absorption (RSA) that recovers with a time constant of 120 ps. We attribute this RSA to excited-state absorption within the singlet system of the King's complex, and we demonstrate that the RSA is completely characterized by a simple three-level model. We find, however, that the material parameters extracted from these picosecond measurements cannot account for the strong optical limiting previously observed in identical solutions of this compound using nanosecond excitation at higher fluences. Picosecond measurements at fluences greater than 200 mJ/cm² reveal the onset of an additional loss mechanism that appears ~1 ns after excitation. The magnitude of this loss depends on both the laser repetition rate and the solvent, indicating that the loss is not directly related to the intrinsic properties of the King's complex but is most likely thermal in origin. Using nanosecond excitation pulses, we have performed angularly resolved transmission and reflection measurements, which reveal strong forward- and backward-induced scattering at these fluences. Furthermore, when the King's complex is incorporated in a solid host, we observe negligible induced scatter and the response is completely described by the singlet parameters extracted from the picosecond measurements. These observations indicate that the nanosecond optical limiter response of solutions of King's complex is dominated by thermally induced scattering.