Rotationally resolved multiphoton ionization photoelectron spectroscopy of the [a 1Δ]3dπ 2Φ and [a 1Δ]5pπ 2Φ Rydberg states of the SH radical

Abstract

Experimental and theoretical results on the rotationally resolved photoelectron spectra of the ͓a 1 ⌬͔3d 2 ⌽(vЈϭ0) and the ͓a 1 ⌬͔5 p 2 ⌽(vЈϭ0) Rydberg states of the SH radical are presented. In particular, for the former state, ionization via a large number of members of different rotational branches is considered. The interplay between experiment and ab initio calculations, including alignment, allows for a detailed interpretation of the results. Asymmetries apparent in the rotational ionic distributions and the observed suppression of transitions involving a large change in angular momentum can be explained on the basis of the theory. © 1997 American Institute of Physics. ͓S0021-9606͑97͒04831-9͔

Rotationally resolved photoionization dynamics of hot CO fragmented from OCS

“…A well-studied class of molecules with large rotational constants are the diatomic hydride radicals such as OH, 11 NH, 12,13 and SH. 14,15 In this work, rotationally resolved photoelectron spectroscopy is carried out on hot CO photofragments produced in the photodissociation of OCS. The rotational constant of CO ϩ in the X 2 ⌺ ϩ ionic ground state is only 1.9677 cm Ϫ1 .…”

Rotationally resolved photoelectron spectroscopy of hot N2 formed in the photofragmentation of N2O

“…Representative cases are stable molecules such as diatomic hydrogen [22][23][24][25] and its isotopomer D 2 , 26,27 and several short-lived diatomic hydride radicals such as OH, 28 NH, 29,30 and SH. 31,32 The present paper is concerned with rotationally resolved laser photoelectron spectroscopy of hot N 2 photofragments using the aЉ 1 ͚ g ϩ intermediate state. The rotational constant of N 2 ϩ in the X 2 ͚ g ϩ ionic ground state is only 1.922 321 cm Ϫ1 .…”

“…33 However, the high rotational excitation of the N 2 fragments following photodissociation of the N 2 O parent accesses ionic rotational levels with high J ϩ , and hence leads to a situation where the ionic rotational spacings exceed the spectrometer resolution. The results of our experiments are compared to those of advanced ab initio quantumchemical calculations, a strategy that has proved its worth in many cases, 28,30,31 and which gives detailed information about the dynamics of the photoionization process. In addition, improved values of rovibrational parameters of the aЉ 1 ͚ g ϩ Rydberg state are obtained.…”

Laser photoelectron spectroscopy: spectroscopy and dynamics of excited states in small and medium‐sized molecules

“…Then, the [a1A]3dn 2(D(v' = 0) state, also situated below the lowest X3C-ionic threshold, will be discussed. This state shows rotationally resolved PE spectra with large asymmetries apparent in the ionic distributions [54]. With the help of ab initio calculations the observed features can be understood in detail.…”

“…However, the effects of alignment following the two-photon absorption to the excited '(D state were included. Since the e/f parities of the rotational levels in the ' (D intermediate state and the u l A ionic state cannot be resolved experimentally, the contributions to the cross-sections from both the e and f parities of each rotational level were summed [54].…”