Vibrational and Electronic Spectra of Matrix-Isolated N3. and N3(1-)

Article abstract of DOI:10.1021/j100325a018

N3. and N3(1-) 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, ν₂=472.7, ν₃=1657.5, and ν₁+ν₃=2944.9 cm^-1 as well as those in two other sites were obtained, and dissociation into N(2D) and N2(1Σ_g(+)) was observed upon 2Σ_u(+)<-2Π_g excitation of N3. at 272 nm.The ν₃ vibrational frequencies of free and ion-paired N3(1-) in a nitrogen matrix are 2003.5 and 2077.8 cm^-1, and their photodetachment thresholds in a mixed nitrogen-argon matrix (ca. 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(1-).The results of similar computations for N3(1+) agree with an extrapolation of the experimental frequencies from N3(1-) and N3. and suggest strongly a value near 1200 cm^-1 for ν₃.