Potential energy surface and thermochemistry for the direct gas phase reaction of germane and water

Abstract

Gas phase reaction between germane GeH₄ and water H₂O was investigated at CCSD(T)/[aug-cc-pVTZ-pp for Ge + Lanl2dz for H and O]//MP2/6-31G(d,p) level. Only the hydrogen elimination channels are monitored. Within the energy range of 100 kcal/mol, we located nine equilibrium and six transition states on the potential energy surface (PES) of the Ge–O–H systems. GeH₄ reacts with H₂O exothermically (by 2.37 kcal/mol) without a barrier to form a non-planar complex GeH₄·H₂O which isomerizes to GeH₃OH·H₂ and H₂GeOH₂·H₂ with a barrier of 44.34 kcal/mol and 53.75 kcal/mol respectively. The first step of hydrogen elimination gives two non-planar species, GeH₃OH and H₂GeOH₂ but germinol GeH₃OH is found to be more stable. Further thermal decomposition reactions of GeH₃OH involving hydrogen elimination have been studied extensively using the same method. The final hydrogen elimination step gives HGeOH which can exist in cis and trans forms. As the trans form is more stable, only the trans form is considered on the potential energy surface (PES) of the reaction. The important thermochemical parameters (∆_rE_tot + ZPE), ∆_rH and ∆_rG for the H₂ elimination pathways are predicted accurately.