The molecular ion NO2 has been stabilized in an argon matrix in sufficient concentration for detection of its antisymmetric stretching fundamental, ν3, at 1244 cm−1 by electron bombardment or photoionization of matrix‐isolated NO2 and by the interaction of an alkali‐metal atomic beam with NO2 in an argon matrix. In contrast to the position of this fundamental in an inert, nonionic environment, a value of approximately 1275 cm−1 is characteristic of the crystalline material. Isotopic data are consistent with a 115° valence angle for NO2, independent of environment. Irradiation of the sample with light of wavelength near 3150 Å leads to the destruction of the NO2 absorption in the studies of the electron bombardment and photoionization of NO2, but not in the experiments in which the alkali metal atoms provide a reservoir of photoelectrons.

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