THE CHARACTERIZATION OF GeH2 AND GeH USING MATRIX ISOLATION INFRARED SPECTROSCOPY

Matrix isolation infrared spectroscopy was used to characterize the fundamental infrared peaks of the germanium hydride species GeH2 and GeH in low temperature argon matrices that result from the vacuum-ultraviolet (VUV) photolysis of germane (GeH4). Experiments were performed by depositing mixtures of GeH4 with argon onto a CsI window cooled to 12 K while simultaneously photolyzing the mixture with 121 nm VUV radiation from a hydrogen resonance lamp. For GeH2, the fundamental infrared peaks are observed at 1839.1 cm(ν3, antisymmetric stretch), 1816.6 cm(ν1, symmetric stretch) and 913.4 cm(ν2, bend). For GeH, the fundamental infrared stretching peak is observed at 1813.4 cm−1. The assignment of the observed peaks is established by performing experiments with isotopic germane (GeD4), by performing matrix annealing experiments (warming to 25 35 K and refreezing to 12 K), by performing mercury-xenon lamp matrix photolysis experiments (200 900 nm), and by comparison to quantum chemical calculations performed at the B3LYP and MP2 levels of theory. This work corrects what appears to be incorrect assignments made in the earlier report of Smith and Guillorya.