Fourier transform infrared and Raman studies on solid nitrogen dioxide: Temperature cycling of ordered, disordered, and multicomponent layers

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Abstract
Fourier transform infrared (FTIR) spectra of nitrogen dioxide layers deposited at various rates and substrate temperatures, are reported. Bands assignable to N2O4(D2h) (ordered and disordered layers), to O=N–O–NO2 ‘‘D’’ and ‘‘D′’’ isomers, to NO+NO−3 nitrosonium nitrate and to the NO2 monomer were observed. The relative amounts of species depends upon deposition conditions. Temperature cycling effects were followed up to 205 K. Solid N2O4(D2h) behaves like a normal, stable molecular solid, its disordered layer exhibiting small frequency shifts, but also being stable with respect to temperature cycling. The observation of NO+NO−3 bands is related to the existence of the D′ isomer and of monomeric NO2. Raman experiments overemphasize the NO+NO−3 form due to resonant enhancement.

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