Journal of Chemical Physics, Vol.110, No.12, 5658-5669, 1999
Electron spin resonance studies of (ScO)-Sc-45-O-17, (YO)-Y-89-O-17, and (LaO)-La-139-O-17 in rare gas matrices: Comparison with ab initio electronic structure and nuclear hyperfine calculations
The first nuclear hyperfine measurements of O-17 (I=5/2) have been made for Sc O-17, (YO)-O-17 and (LaO)-O-17 in their X (2)Sigma ground electronic states. These metal oxide radicals were generated by the pulsed-laser vaporization of the metals in the presence of O-16(2)/O-17(2) and trapped in neon and argon matrices for electron spin resonance investigations. The fully resolved A tensors of the metal and O-17 were compared with ab initio theoretical calculations-a comparison previously reported only for the ScO radical. The computational methods employed were unrestricted Hartree-Fock, density functional theory (DFT), and restricted open-shell Hartree-Fock. Having the metal and O-17 hyperfine interactions available has permitted a more thorough description of the electronic structure and charge distribution in these metal oxide molecules. An electronic structure comparison with the AlO, GaO, and InO radicals has also been made. Reasonably good agreement between the observed and calculated values of A iso and A dip were achieved with the DFT method providing the closest agreement.