Free Radical Reactions of N2O Molecules

Experimental data are presented on the spectral (ESR, IR, and optical) and thermochemical characteristics of a complex between the (≡Si–O)3Si.radical and an N2O molecule. The rate constants of separate reactions in the systems (≡Si–O)3Si.+ N2O and (≡Ge–O)3Ge.+ N2O are found. The results of quantum chemical calculations of potential energy surfaces and spectral characteristics are presented for the following systems: H.+ N2O, H3C.+ N2O, H3Si.+ N2O, F2HSi.+ N2O, F3Si.+ N2O, and F3Ge.+ N2O. The latter three systems served as molecular models for experimentally found systems. Based on experimental and theoretical data, the product of N2O addition to (≡Si–O)3Si.has the structure ≡Si–N=N–O.. The reactions of free radicals H., H3C., H3Si., F2HSi., F3Si., (≡Si–O)3Si., and (≡Ge–O)3Ge.with N2O are compared. The spectrum of optical absorbance of the (≡Si–O)3Si–O.radical is recorded and qualitatively characterized.