Two-colour pulsed Raman studies of the lowest excited singlet state of tetraphenylporphyrin: band assignments and electronic structure

Abstract

The resonance Raman spectra of the lowest lying singlet (S 1 ) state of free-base tetraphenylporphyrin and seven of its isotopomers were recorded under pump-and-probe conditions with a time delay of −2 ns between pump and probe laser pulses. In the S 1 spectra of the isotopomers, as in the ground state, there are dramatic splittings of what appear to be single bands in the natural isotopic abundance spectrum. The most structurally significant bands of the S 1 state were assigned on the basis of the isotope data. In some cases it was necessary to curve fit unresolved bands in the excited-state spectra in order to account for observed intensity ratios and to rationalize isotope shifts. The changes in band positions on excitation to the S 1 state were compared with those from earlier studies on the T 1 state. The changes in band positions were found to be similar for both excited states. Most notable was the similar shift in n 2 , the most widely used marker band for orbital character. The data are interpreted as implying that the lowest lying singlet state is a configuration interaction admixture of b 1u b 2g Y a u b 3g configurations with the coefficients weighted heavily in favour of b 1u b 2g , which is the configuration of the T 1 state. EXPERIMENTALTR 3 spectra were obtained using two pulsed Nd : YAG lasers (Spectra-Physics DCR2 and GCR3) with pump and probe wavelengths of 532 nm (7-9 ns duration) and 447 nm (5-7 ns duration, second Stokes Raman