Journal of Chemical Physics, Vol.111, No.21, 9568-9573, 1999
A characterization of vibrationally and electronically excited NO2+ by high-resolution threshold photoionization spectroscopy
The pulsed-field ionization zero-electron kinetic-energy (PFI-ZEKE) threshold photoionization spectrum of NO2 from 9.58 to 20 eV is obtained using vacuum ultraviolet synchrotron radiation by means of the Chemical Dynamics Beamline at the Lawrence Berkeley National Laboratory Advanced Light Source. The high resolution afforded by PFI threshold discrimination yields new or refined spectroscopic constants for a number of known excited states of the cation, including the first estimate of the A rotational constant in the a B-3(2) state, as well as new fundamental frequencies for the A (1)A(2) and B B-1(2) states, a precise determination of the singlet-triplet splitting in the c B-3(1)-C B-1(1) complex and the first observations of the states, d (3)A(1) and D B-1(2). Most significantly, ZEKE photoelectron detection resolves vibrational structure in the linear X (1)Sigma(g)(+) ground state of NO2+. Vibrational positions in the first electron volt of the spectrum are found to conform with the predictions of a Hamiltonian that includes Fermi resonance and other anharmonic terms derived from earlier multiresonant laser spectroscopic experiments on the lower bending excited states.