The role of electronic and geometric factors in ‘‘proton tunneling:’’ A comparative study of tropolone and 9-hydroxyphenalenone by threshold photoelectron spectroscopy.

High resolution two-color threshold photoelectron spectra of tropolone and 9-hydroxyphenalenone (9-HPO) isolated in a free jet expansion have been measured to study the proton tunneling phenomena in the cation ground state (D0). The tunneling splitting widths of the D0 zeroth vibrational level for the both molecules lie within our experimental accuracy (2 cm-1), indicating that the proton tunneling is inhibited when compared to that obtained in their respective neutral states. By means of a comparative study of these two molecules, the tunneling inhibition has been explained in terms of a large contribution from the electronic factor which represents the changes in charge distribution of the π electrons upon ionization. The geometric factor, which is associated with the ring planarity is less important in determining the rate of tunneling in the D0 state. In the case of tropolone, we have found that the measurement of an out-of-plane skeletal vibration in various electronic states make it possible to describe the tunneling path at a higher level than a simple one-dimensional description. Moreover, the adiabatic ionization energies of 9-HPO and the deuterated 9-HPO have been determined accurately to be 65 338±5 cm-1 (8.1009±0.0006 eV) and 65 350±5 cm-1 (8.1024±0.0006 eV), respectively. [ABSTRACT FROM AUTHOR]