Polarization spectroscopy of gaseous tropolone in a strong electric field

We report studies of polarization spectroscopy of gaseous tropolone in a strong electric field using resonantly enhanced multiphoton ionization. The electric field induces localization of the tunneling proton between the two equivalent oxygen atoms. As a result, the C2v symmetry of the molecular frame is broken, and the parity selection rule is violated. The field induced transitions are type A with transition dipoles perpendicular to those under field free conditions. The polarization ratios, i.e., the ratios of the overall excitation yield under different polarizations of the resonant laser, thus deviate from those of a pure type B transition. In a field of 60 kV/cm, the experimental polarization ratio implies an essentially equal mixture of type B and type A transitions. Moreover, the induced transitions overlap with the two field-free subbands, and the resulting intensity ratios between the two subbands demonstrate dependence on the applied electric field. These observations can be qualitatively modeled using a quantum mechanical approach by assuming a two level system. A puzzling result is the magnitude of the transition dipole of the induced transition, which is proven to be essentially linearly dependent on the applied electric field.