Rotationally resolved photoelectron spectra in resonance enhanced multiphoton ionization of HCl via the F ^1Δ_2 Rydberg state

Abstract

Results of studies of rotational ion distributions in the X  ^2Π_(3/2) and X  ^2Π_(1/2) spin‐orbit states of HCl^+ resulting from (2+1’) resonance enhanced multiphoton ionization (REMPI) via the S(0) branch of the F  ^1Δ_2 Rydberg state are reported and compared with measured threshold‐field‐ionization zero‐kinetic‐energy spectra reported recently [K. S. Haber, Y. Jiang, G. Bryant, H. Lefebvre‐Brion, and E. R. Grant, Phys. Rev. A (in press)]. These results show comparable intensities for J^+ = 3/2 of the X  ^2Π_(3/2) ion and J^+ = 1/2 of the X  ^2Π_(1/2) ion. Both transitions require an angular momentum change of ΔN = −1 upon photoionization. To provide further insight into the near‐threshold dynamics of this process, we also show rotationally resolved photoelectron angular distributions, alignment of the ion rotational levels, and rotational distributions for the parity components of the ion rotational levels. About 18% population is predicted to occur in the (+) parity component, which would arise from odd partial‐wave contributions to the photoelectron matrix element. This behavior is similar to that in (2+1) REMPI via the S(2) branch of the F  ^1Δ_2 state of HBr and was shown to arise from significant l mixing in the electronic continuum due to the nonspherical molecular ion potential. Rotational ion distributions resulting from (2+1) REMPI via the S(10) branch of the F  ^1Δ_2 state are also shown.