Lawrence Berkeley National Laboratory

Mass-analyzed threshold ionization (MATI) spectroscopy using synchrotron radiation (Advanced Light Source, Lawrence Berkeley National Laboratory) has been performed for Ar, N2, O2, N2O, H2O, C2H2, and C6H6. MATI allows for a better determination of ionization energies compared to those derived from photoionization efficiency curves traditionally used in synchrotron photoionization mass spectrometry. The separation of the long-lived Rydberg state from the directly-formed prompt ion, essential for a meaningful MATI spectrum, has been accomplished by employing an arrangement of ion optics coupled to unique electric-field pulsing schemes. For Ar, a number of resolved bands below the ionization energy are observed, and these are ascribed to high-n,l Rydberg states prepared in the MATI scheme. The first vibrational state resolved MATI spectra of N2 and O2 are reported and spectral characteristics are discussed in comparison with previously-reported threshold photoelectron spectroscopic studies. While MATI performed with synchrotron radiation is intrinsically less sensitive compared to laser based sources, this work demonstrates that MATI spectroscopy performed with widely tunable VUV radiation is a complementary technique for studying the ionization spectroscopy of polyatomic molecules.