Matrix-Isolation Study of the Interaction of Electrons and Alkali Metal Atoms with Various Nitrogen Oxides. Infrared Spectra of the Species NO−, NO2−, and N2O2−

Abstract

The infrared spectra which result when samples of NO2 are codeposited with the various alkali metals in an argon matrix at 4 or at 14°K are consistent with the occurrence of strong charge-transfer interaction. In addition to isolated NO2−, previously identified in this system, ion pairs of general formula Mx+NO2− are stabilized. When NO is substituted for NO2, the infrared spectrum of the initial deposit shows an absorption between 1350 and 1375 cm−1 which can be assigned to the NO− stretching fundamental of Mx+NO− ion pairs, in good agreement with the vibrational spacing recently reported for ground-state NO− in the gas phase. Weak charge-transfer interaction occurs between alkali-metal atoms and N2O in an argon matrix environment. Results of the present experiments can be explained by postulating that the upper, predominantly ionic state of the charge-transfer complex decomposes producing O−, which may diffuse through the matrix. A new absorption which appears at 1205 cm−1 has tentatively been assigned to ν4(b1) of a planar O2N=N− anion. In studies of the interaction of sodium atoms with Ar:NO:N2O mixtures, mercury-arc irradiation of the sample leads to the appearance not only of the N2O2− absorption, but also of absorptions due to isolated NO2− and to Nax+NO2−.

Reactions of Laser-Ablated Iron Atoms with N2O, NO, and O2 in Condensing Nitrogen. Infrared Spectra and Density Functional Calculations of Ternary Iron Nitride Oxide Molecules

“…The latter three bands show mixed oxygen isotopic components and similar isotopic ratios with argon matrix bands at 1243.7 and 1205.5 cm -1 assigned earlier to NO 2 -and NNO 2 -. 19 The latter bands, and the 792.4 cm -1 band due to isolated O 3 -, 20 show that electrons are produced in these experiments. However, note that the NO 2 band at 1616.0 cm -1 is 1 order of magnitude stronger than the NO 2 -band at 1236.8 cm -1 , which suggests that electron capture processes play only a minor role in these experiments.…”

Electronic Absorption Spectra of Neutral Pentacene (C22H14) and Its Positive and Negative Ions in Ne, Ar, and Kr Matrices

“…Similar observations of the concurrent production of anions in matrices in both isolated sites and in sites where there is significant interaction with the alkali metal cation have been previously reported. 24 We discuss below the pre-and postphotolysis spectra of pentacene isolated in alkali atom-doped matrices.…”

Abinitio study on radical anions of nitro compounds

“…The comparison between assigned vibrational modes reveals variations that reflect the structural reorganization occuning upon electron attachment. The IR spectrum of the anion NO1-produced in low temperature matrix by electron transfer processes (37), shows that the v3 stretching mode (1240 cm-I) is appreciably shifted with respect to the frequency of the neutral NO? (1617 cm-') (38).…”