Vacuum-Ultraviolet Photolysis of GeH3Cl; the Infrared Spectrum of Matrix-Isolated GeH2Cl

The vacuum‐ultraviolet photolyses of GeH₃Cl and GeD₃Cl in argon and carbon monoxide matrices have been performed between 4 and 25°K. The major product of photolysis appears to be the free radical species GeH₂Cl, and possibly some GeHCl as a result of secondary photolysis. Evidence that H atom detachment plays a major role in the photodissociation process is obtained by the formation of HCO in carbon monoxide matrix experiments. All six fundamental vibrational frequencies of GeH₂Cl are observed and assignments are made for ${\nu }_2({\mathrm{GeH}}_2\mathrm{valence\; bend}{\mathrm{),\; \nu }}_3(\mathrm{GeCl\; stretch}{\mathrm{),\; \nu }}_4({\mathrm{GeH}}_2\mathrm{wag}\mathrm{),}\mathrm{and}{\nu }_6({\mathrm{GeH}}_2\mathrm{twist})$ . Tentative assignments for the GeH stretching frequencies ${\nu }_1(\mathrm{sym\; stretch})$ and ${\nu }_5(\mathrm{antisym\; stretch})$ are made. A normal coordinate calculation using a six‐constant valence potential function suggests that the molecule is pyramidal with approximate ${\mathrm{sp}}^3$ hybridization. The structure, bonding, and thermodynamlc properties of GeH₂Cl are also discussed and compared with other Group IV species.