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Probing Isomerization Dynamics via a Dipole-Bound State
Yuzhu Lu1, Rulin Tang1, Rui Zhang1
1Department of Physics, State Key Laboratory of Low Dimensional Quantum Physics, Tsinghua University, Beijing, 100084, China.
Abstract:
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.
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