Pulsed-ramped-field-ionisation zero-kinetic-energy photoelectron spectroscopy of the metastable rare-gas atoms Ar, Kr and Xe.

The photoionisation of the metastable rare-gas atoms Rg = Ar, Kr and Xe is investigated at the Rg + […]( n s) 2 ( n p) 5 2 P 3/2 ← Rg[…]( n s) 2 ( n p) 5 (( n + 1)s) 13 P 2 photoionisation threshold ( n = 3, 4 and 5 for Ar, Kr and Xe) using the technique of pulsed-ramped-field-ionisation zero-kinetic-energy (PRFI-ZEKE) photoelectron spectroscopy. This technique, which monitors the field ionisation of high Rydberg states induced by a slowly growing electric-field ramp after a prepulse of opposite polarity, was recently introduced to record photoelectron spectra with high resolution and high sensitivity [Harper, Chen, Boyé-Péronne and Gans, Phys. Chem. Chem. Phys. , 2022, 117 , 9353]. A tunable UV laser system with a bandwidth of 30 MHz is used here to establish the factors determining the resolution and overall accuracy of this new method. In particular, the effects of stray electric fields, and of the magnitude of the prepulse and the field ramp on PRFI-ZEKE photoelectron spectra are studied by combining experiments with numerical simulations of the field-ionisation of high Rydberg states and of the electron flight times from the ionisation spot to the detector. A spectral resolution of 0.05 cm -1 is demonstrated in the photoelectron spectrum of metastable Ar.