Electron spin resonance matrix isolation studies of 27Al16,17O, 69,71Ga16,17O and 115In16,17O: Observed hyperfine interactions compared with ab initio theoretical results

ACS Citation

Knight, L. B.; Kirk, T. J.; Herlong, J. O.; Kaup, J. G.; Davidson, E. R. Electron spin resonance matrix isolation studies of 27Al16,17O, 69,71Ga16,17O and 115In16,17O: Observed hyperfine interactions compared with ab initio theoretical results. J. Chem. Phys. 1997, 107, 7011-7011.

Abstract

Electron spin resonance(ESR) studies are reported for Al 16,17 O , Ga 16,17 O , and In 16,17 O isolated in neon matrices at 4 K. Except for Al 16 O , no previous ESR measurements have been reported for these X-€‰ 2 Σ diatomic radicals. The pulsed laservaporization of the metals in the presence of 16 O 2 and 17 O 2 produced high quality ESR spectra of these metal oxide radicals whose nuclear hyperfineinteractions (A tensors) were fully resolved for both the metal and oxygen nuclei. An analysis of the experimental spin densities in combination with different types of theoretical calculations provided detailed information concerning the electronic structure trends going down this metal oxide group. Increased p -orbital spin density on oxygen was observed for the heavier metal oxide radicals. Nonrelativistic ab initio calculations with an extended basis set and the UB3LYP method reproduced the trends in the isotropic and dipolar hyperfineinteractions. All-electron CI calculations, restricted open-shell Hartree-Fock (ROHF) wave functions, and unrestricted Hartree-Fock wave functions gave results very different from experiment and from each other for the isotropic interaction. All calculations were in fair agreement with each other for the dipolar interaction and provided an assignment of the sign for that term.

Source Name

Journal of Chemical Physics

Publication Date

1-1-1997

Volume

107

Issue

18

Page(s)

7042-7048

Document Type

Citation

Citation Type

Article

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