Journal of Physical Chemistry, Vol.99, No.46, 16867-16876, 1995
N-14 Quadrupole and Hyperconjugative Hyperfine Coupling in 2-Aminoethyl Hydrogen Sulfate X-Irradiated at 295 K - Single-Crystal ENDOR Analysis - UHF-Indo Mo Calculations
Single crystals of 2-aminoethyl hydrogen sulfate (AES), H3N+CH2CH2OSO3-, were X-irradiated at 295 K and studied using X-band EPR, ENDOR, and FSE (EI-EPR) spectroscopy. Results of the analysis of N-14 interactions in the radical H3N+CH2CHOSO3- are reported. A program was developed for the analysis of the N-14 hyperfine and quadrupole coupling tensor from single-crystal ENDOR data. An error propagation routine was developed that represents a refinement of those previously reported in the literature. The signs of the hyperfine coupling tensor principal values were deduced from interpretation of the quadrupole tensor employing the Townes-Dailey approach. The large positive hyperfine coupling to the beta-position N-14 nucleus is attributed to hyperconjugation. This is confirmed through UHF-INDO calculations with subsequent calculation of the complete hyperfine coupling tenser. The beta-N-14 isotropic interaction is described by a Heller and McConnell type ’cos(2) theta’ rule analogous to the relation observed for beta-protons, beta-F-19, and beta-P-31. The experimental estimates for the parameters B-0 and B-2 are supported by other recent observations and by the UHF-INDO calculations.
Keywords:EIGENVECTORS;EIGENVALUES