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

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.

High-pressure stability, transformations, and vibrational dynamics of nitrosonium nitrate from synchrotron infrared and Raman spectroscopy

“…Ϫ increases with compression. However, the far-IR lattice mode had not been observed previously, either in IR spectra of N 2 O 4 at atmospheric pressure [13][14][15] or in NO ϩ NO 3…”

Identification of Neutral and Charged NxOySurface Species by IR Spectroscopy

“…As a result, the NEO bond order becomes ϳ3 and the NEO stretching modes are shifted to 2391-2102 cm Ϫ1 [120,161]. As has been noted, NO can easily lose its unpaired electron situated on an antibonding orbital and thus be converted into NO ϩ .…”

Fourier transform infrared spectrum of well ordered solid dinitrogen tetroxide

“…10 The quartet can, however, be readily reconstructed in layers formed by fast, low temperature depositions. 3 The additional components are, then, not due to dispersive crystal coupling effects,1O but rather to solid disorder effects.…”