Two-photon spectroscopy of the Schiff base of all-trans-retinal. Nature of the low-lying π π* singlet states

Abstract

The two-photon excitation spectrum of all-trans-N-retinylidene-n-butylamine (ATRSB) in EPA at 77 K is obtained over the wavelength region from 370 to 455 nm (λex/2) using linearly polarized light. The two-photon excitation maximum is observed at ~422 nm (λex/2) and is red shifted ~2800 cm−1 from the one-photon absorption maximum at ~377 nm. We assign the two-photon excitation spectrum to the "1Ag*−" ← S0 transition which indicates that the "1Ag*−" π π* state lies below the "1Bu*+" π π* state in ATRSB. Comparisons of the one-photon absorption, two-photon excitation, and fluorescence spectra of ATRSB with the corresponding spectra of all-trans-retinal are presented. PPP-CISD calculations correctly predict the directions but not the magnitudes of the blue shifts of the π π* excited state transition energies in going from all-trans-retinal to ATRSB. We postulate that the "1Ag*−" π π* state is preferentially stabilized relative to both the ground state and the nearby "1Bu*+" state by hydrogen bonding to solvent molecules. Comparison of the spectra reported here with the two-photon spectra of rhodopsin provides further evidence that the chromophore in rhodopsin is protonated.