Probing Isomerization Dynamics via a Dipole-Bound State.

The observation of molecular isomerization dynamics is a long-standing goal in physical chemistry. The loosely bound electron in a dipole-bound state (DBS) can be a messenger for probing the isomerization of the neutral core. Here we study the isomerization dynamics of the salt dimer (NaCl) 2 from linear to rhombic via a DBS using cryogenic photoelectron spectroscopy in combination with ab initio calculations. Although the energy level of the DBS is below the electron affinity of the linear (NaCl) 2 , (NaCl) 2 - in its DBS can autodetach due to the linear-to-rhombic isomerization. (NaCl) 2 - in the ground DBS has a relatively long lifetime of a few nanoseconds due to the quantum tunneling through a potential barrier during the transformation from linear to rhombic. In contrast, the vibrationally excited DBS has a much shorter lifetime on the order of picoseconds. The energy distribution of autodetachment electrons has an unexpected characteristic of the thermionic emission.