F. Merkt, COLLISIONAL AND ELECTRIC-FIELD EFFECTS IN THE DELAYED PULSED-FIELD IONIZATION ZERO-KINETIC-ENERGY PHOTOELECTRON-SPECTRUM OF ARGON, The Journal of chemical physics, 100(4), 1994, pp. 2623-2628
The pulsed field ionization (PFI) zero-kinetic-energy (ZEKE) photoelec
tron spectrum of argon has been recorded in the region of the transiti
on from the ground neutral state (S-1(0)) to the first two ionization
limits corresponding to the two spin-orbit levels (P-2(3/2) and P-2(1/
2)) of the ground state of the ion. The high-n Rydberg states (85 < n
< 200) belonging to the series converging to the upper spin-orbit stat
e have a lifetime which is more than 50 times longer than expected for
the optically accessible ns' and nd' series. A series of experiments
with pulsed and continuous electric fields of different magnitude show
s that the nature-and the lifetimes of the high-n Rydberg states probe
d by ZEKE spectroscopy depend critically on the experimental condition
s, in particular on electric held and collisional effects. New experim
ental results are presented which contribute to a better understanding
of the mechanisms which lead to the formation of the unexpectedly lon
g-lived states which are observed in ZEKE spectroscopy.