Infrared predissociation spectrum of the H3+ ion. II
Authors: Carrington Alan , McNab Iain R. , West Yvonne D. 
Published: July 2002

The infrared predissociation spectrum of the H3+ ion has attracted considerable attention; theoretical models have been developed which account for many of the observed features and which make further predictions. This paper describes the results of experiments designed to test these predictions. The spectrum is recorded by bringing a mass-selected H3+ ion beam into parallel or antiparallel coincidence with a cw carbon dioxide infrared laser beam. In the earlier work, 27 000 lines were observed over the range 874–1094 cm−1, each line being recorded by detecting H+ fragment ions produced by predissociation. The spectrum varied according to the H+ kinetic energy window selected, and it was proved that many of the lines arise from metastable states of H3+ lying above the H2+H+ dissociation limit. The spectrum showed no immediately recognizable pattern, but low resolution convolutions revealed the existence of a coarse-grained structure of four main peaks. The isotopic species H2D+ and D2H+ showed similarly complex spectra which, however, differed depending on whether H+ or D+ fragments were detected. The most important conclusion from subsequent theoretical models is that the metastable states involved are in a region of classical chaos and hence cannot be simply assigned in terms of vibrational modes. However, the coarse-grained spectrum is associated with the remnants of a periodic orbit in which quasilinear H3+ undergoes a large amplitude bending motion.
Rotational angular momentum barriers lead to trapping of these essentially regular states, which are embedded in a classically chaotic manifold. Semiclassical trajectory studies and three-dimensional quantum mechanical calculations are consistent with each other. Our present experimental methods are described and questions concerning reproducibility are addressed. We describe new measurements over the range 964–992 cm−1 spanning the position of one of the peaks observed earlier in the convoluted spectrum. The H3+ spectrum is recorded for a series of different H+ kinetic energy windows and the results are summarized in bar charts. Convolutions of the data recorded for H+ ions with very small center-of-mass kinetic energies are consistent with the earlier results and with theoretical predictions, but also reveal additional structure. Convolutions for large H+ kinetic energies (≥500 cm−1) reveal less evidence of characteristic structure. Measurements over the region 1025–1045 cm−1 are also described; they are only for very small H+ kinetic energy release, but the linewidths are also tabulated. Most of the metastable states of H3+ predissociate predominantly through a single channel, but examples of multiple dissociation channels have also been recorded. Direct measurements of some predissociation lifetimes are presented. Selected regions of the spectra of D2H+ and H2D+, measured by recording H+ and D+ fragments separately with kinetic energy windows from 0 to 3000 cm−1, are described. The results are in excellent agreement with theoretical predictions, as also are measurements of the background spontaneous predissociation.