Spectroscopy of metastable species in a free-jet expansion: the β ← A transition in IBr

Abstract

The A 1(3Π) state of IBr is observed in a free-jet expansion of IBr in Ar, following photolysis with ArF laser irradiation. Laser excitation spectra are obtained for the β 1(3P2) ← A transition in medium (0.5 cm−1) and high (0.08 cm−1) resolution. Sixteen ν′–ν″ bands recorded in high resolution are rotationally analyzed, providing the first detailed characterization of the lowest three νlevels in the A state. An additional ~50 bandheads in the ν″ = 0 and 1 progressions are recorded for both I79Br and I81Br. The new data, which sample ν′ levels in the range 31–71, are combined with existing information for low ν in the β state to provide improved constants for the β state. These results are merged with least-squares parameters from a detailed reanalysis of existing data for the A and X(1Σ+) states to yield spectroscopic parameters valid for ν = 0–20 in the X state and ν = 0–26 in the A state. Among these results are the first precise estimates of the equilibrium parameters in the A state: Te = 12 369.68 (14) cm−1, ωe = 134.22 (13) cm−1, Be = 0.042 40 (5) cm−1, Re = 2.8583 (16) Å.