Electronic spectroscopy of phthalocyanine in a supersonic jet revisited.

Spectroscopic investigation of phthalocyanine in the gas phase has tremendously profited from molecular beam spectroscopy. Isentropic expansion succeeds in reducing the population of rovibrational states to the vibrational ground state so that only low energy rotational states remain populated. However, with respect to UV-vis spectroscopy the pioneers of molecular beam spectroscopy came to the discouraging conclusion that the information contained in the rotational structure of a large molecule is minimal, and even if the rotational structure could be resolved with great effort, the results are unlikely to be worth the difficulty [Levy, Annu. Rev. Phys. Chem. , 1980, 31 197-225]. Just over 4 decades later we would like to announce that the result is worth the effort, indeed. Even without full line resolution, the rotational structure at the electronic band origin of phthalocyanine provides deep insight into configurational details of phthalocyanine for both electronic states. These details serve as gas phase compliment to the investigation of microsolvation in superfluid helium droplets. To the best of our knowledge this is the largest molecule ever analyzed by means of its rotational degrees of freedom.