Vibrational and electronic spectra of matrix-isolated N3· and N3-

N3· and N3^- were formed upon the bombardment of a N2 matrix with kiloelectronvolt-energy fast atoms and/or ions. The vibrational frequencies of N3· in the most stable site, v2 = 472.7, v3 = 1657.5, and v1 + v3 = 2944.9 cm^-1, as well as those in two other sites were obtained, and dissociation into N(²D) and N2(¹Σg⁺) was observed upon ²Σu⁺ ← ²Πg excitation of N3· at 272 nm. The v3 vibrational frequencies of free and ion-paired N3^- in a nitrogen matrix are 2003.5 and 2077.8 cm^-1, and their photodetachment thresholds in a mixed nitrogen-argon matrix (∼2:1) are 4.5 and 3.4 eV, respectively. The experimental frequencies are compared with the results of Hartree-Fock computations for N3· and N3^-. The results of similar computations for N3⁺ agree with an extrapolation of the experimental frequencies from N3^- and N3· and suggest strongly a value near 1200 cm^-1 for v3. © 1988 American Chemical Society.

Duke Scholars

Author Julio Cesar Facelli Biostatistics & Bioinformatics, Division of Translational Bi ...