A new detection scheme for synchronous, high resolution ZEKE and MATI spectroscopy demonstrated on the Phenol·Ar complex

We present a new detection scheme for high resolution mass analyzed threshold ionization (MATI) spectroscopy which utilizes fractional Stark state selective electric field ionization of high-n Rydberg states. The method represents a significant advance over previous approaches to MATI spectroscopy, which have been characterized by their low resolution compared to zero kinetic energy (ZEKE) photoelectron spectroscopy. In addition, the scheme can be used to synchronously obtain electrons and ions originating from the same Rydberg states, facilitating the acquisition of synchronous, high resolution ZEKE and MATI spectra. We demonstrate the technique by obtaining MATI dissociation spectra of the phenol·Ar complex, which provide dissociation energies of 364±13, 397±13, and 535±3 cm−1 for the S0, S1 and D0 states, respectively.