Electronic spectroscopy of biphenylene inside helium nanodroplets

We have recorded the S1 <-- S0 electronic spectra of Biphenylene and its Ar and O2 van der Waals complexes inside helium nanodroplets using beam depletion detection. In general, the spectrum is similar to the previously reported high-resolution REMPI spectrum. The zero phonon lines, however, are split similar to the previously reported tetracene case. The calculated potential energy surface predicts that helium atoms can simultaneously occupy all equivalent global minima positions. Therefore, it appears that the splitting cannot be explained either by different isomers or by tunneling. Furthermore, surprisingly the splitting is retained for the Ar van der Waals complexes (and possibly for the O2 complex as well). This case suggests that the current models of the origin of zero phonon line splitting and the helium solvation are incomplete.