Matrix effects on radiative and radiationless rates of NBr b 1Σ+ and a 1Δ trapped in solid argon

Abstract

NBr in solid argon has been excited to the b 1Σ+ state with a pulsed tunable dye laser. In addition to the well-known fluorescence spectrum of the b state, infrared emission from the vibrationally relaxed a 1Δ state was detected at 1086 nm. Three major trapping sites were resolved in absorption and fluorescence excitation spectra of the b–X system. Additional sites could be identified in the excitation spectrum of the a state, which is populated via the b state by internal conversion. There is a weak site effect on the lifetime of the vibrationally relaxed b state, which varies between 40 and 30 μs. Vibrational relaxation rates in the b state show a stronger site dependence. Internal conversion from b 1Σ+ to a 1Δ accounts for <0.1% to at least 17% of the decay rate of NBr b 1Σ+, v=0. Orbitally forbidden transitions to the X10+ component of the ground state were identified 23.0 to 25.5 cm−1 on the high-energy side of the more intense a 1Δ→X21± transition of several sites. The lifetime of the a state varies between 152±12 ms in the least perturbed site and 121±15 ms in the site with the strongest a 1Δ→X10+ forbidden component. NBr trapped in double vacancies of pure fcc argon, of single stacking faults, and of multiple stacking faults (hcp pockets) in argon, can account for the sites.