Electron spin resonance rare gas matrix studies of 12CO2-,13CO2-, and C17O-2: Comparison with ab initio calculations
Knight, L. B.; Hill, D. W.; Berry, K.; Babb, R. M.; Feller, D. Electron spin resonance rare gas matrix studies of 12CO2-,13CO2-, and C17O-2: Comparison with ab initio calculations. J. Chem. Phys. 1996, 105, 5672-5672.
The 12C16O2-, 13C16O2-, 12C17O2-, and 12C16,17O2- radical anions have been generated by four independent methods and isolated in neon and argon matrices for detailed ESR(electron spin resonance) investigations. Included with these experimental measurements for the various magnetic parameters of CO-2 are high level ab initio calculations (MR SD-CI and others) of the 13C and 17O hyperfine A tensors. Some of the calculations included the effects of a 42-atom on cage on the electronic structure of CO-2. Previous ESR studies of CO-2 have been conducted in more perturbing environments, such as ionic crystals, where the close proximity of the counter cation can alter the anion's properties. A comparison of the earlier measurements in more interactive materials with these theoretical and rare gas matrix results reveals a significantly different distribution of the spin density. The neon magnetic parameters (MHz) for CO-2 are gx =2.0018, gy=1.9964, gz =2.0010; for 13C, Ax =320.4, Ay =296.1, Az =394.5; for 17O, Ax =-81.6, Ay =-74.9 and Az =-151.8. The argon results are similar to these neon values; isotropic spectra in argon were also observed at elevated temperatures that yielded giso and Aiso parameters consistent with the low temperature (4 K) anisotropic spectra.
Journal of Chemical Physics