Theoretical and electron spin resonance studies of the the H···‹…H, H···D, and D···‹…D spin-pair radicals in rare gas matrices: A case of extreme singlet-triplet mixing

ACS Citation

Knight, L. B.; Rice, W. E.; Moore, L.; Davidson, E. R.; Dailey, R. S. Theoretical and electron spin resonance studies of the the H···‹…H, H···D, and D···‹…D spin-pair radicals in rare gas matrices: A case of extreme singlet-triplet mixing. J. Chem. Phys. 1998, 109, 1409-1409.

Abstract

The H···‹…H, H···D, and D···‹…D spin-pair radicals have been thoroughly investigated in neon, argon, krypton, and xenon matrices near 4 K by electron spin resonance (ESR). A theoretical model has been developed that treats these spin-pairs as weakly interacting atoms. The model includes the effects of 3Σ/1Σ mixing in the analysis of the observed ESR spectral results and yields a consistent set of magnetic parameters for these three isotopomers in all four rare gas hosts. The consideration of H atoms interacting with other H atoms over a distribution of internuclear distances in the rare gas lattice is included in the theoretical and experimental analyses. Application of the model to earlier ESR results for H···CH3 reveals a value for its Heisenberg exchange interaction (J) which is found to be considerably larger than that for the H···H spin-pair. The effects of methane and neon on the J value are calculated for these spin-pairs. The H···H case is unusual in that the nuclear hyperfineinteraction (A) is considerably larger than D (the anisotropic dipole-“dipole magnetic interaction between electrons) which is much larger than J. The H···H spin-pairs exhibit internuclear distances greater than 7 Å and have the following magnetic parameters (MHz) based upon this model of -œweakly interacting atoms;- giso =2.0016, Aiso =1426, D=-200, and J=6. Since a distribution of distances is involved, other spin-pairs would be separated by even greater distances in the matrix and thus have smaller absolute values of D and J.

Source Name

Journal of Chemical Physics

Publication Date

1-1-1998

Volume

109

Issue

4

Page(s)

2732-2738

Document Type

Citation

Citation Type

Article

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