Enhanced Femtosecond Nonlinearities and Multiphoton Absorptions in Discrete Bands of Porphyrins.

Optical nonlinearities of discrete absorption energy levels of one of the typical heterocyclic aromatic molecules, free-base porphyrins, have been probed over a broad spectral region (400-1600 nm) utilizing intense femtosecond pulses. A wide range of strong one- and multiphoton-induced nonlinear absorptions of both the blue-end Soret (B) band (a → b) and red-end orbital mixing split quasi-allowed Q-bands (Q(0,0; 0,1), Q(0,0; 0,1), a → e) are critically probed and reported. During the resonant excitation within B- (400 nm) and Q-bands (600-750 nm), the nonlinear absorption has become predominant by the saturation of absorption (SA) of the one-photon absorption (1PA) process due to ground-state bleaching. At nonresonant wavelengths, it is dominated by the reverse saturation of absorption (RSA), involving various nonlinear processes of two-, three-, and four-photon (2PA, 3PA, and 4PA) absorptions, either to B- or Q-bands (1100-1600 nm). The laser intensity-dependent nonresonant (2PA, 800 nm) excitations for the prominent B-band show a distinct cross-over from SA to RSA, contributed by the excited-state absorption (ESA) utilizing a three-photon induced (3PA) process, whereas resonant (1PA, 400 nm) excitation reveals a systematic strong SA process. Both wavelength- and intensity-dependent nonlinear refractive index studies exhibit positive electronic Kerr-based self-focusing effects, with prominent contributions of nonlinear absorption and higher-order effects. The spectrally discrete, highly intense laser probing of individual energy bands and the consequent variety of nonlinearities can be broadly generalized for many free-base porphyrins and metalloporphyrins. The present studies provide a strong foundation and new insight into the broad categories of macrocycles, such as porphyrins and phthalocyanines, for myriad applications in nonlinear optics and bio/optophotonics.