Journal of the American Chemical Society, Vol.116, No.9, 3967-3972, 1994
Interrelationship Between Conformation and Theoretical Chemical-Shifts - Case-Study on Glycine and Glycine Amide
The gauge independent atomic orbital (GIAO) method was used to explore the change in the chemical shift (Delta delta) with respect to the dihedral angle for glycine, H2NCH2COOH (1), and glycine amide, H2NCH2CONH2 (2), at the GIAO-SCF/6-311G**//RHF/6-31G*, GIAO-SCF/6-311G**//MP2/6-31G*, and GIAO-MP2/6-311G**//MP2/6-31G* levels of theory. The absolute chemical shielding depends strongly on the geometry and the level of theory at which the NMR chemical shielding is calculated. The change of the chemical shifts as a function of the backbone angle psi, however, depends only slightly on the level of theory. Both 1 and 2 are able to reproduce the difference in the chemical shifts for the methylene carbon (C-alpha) that is found for the alpha-helix and the beta-pleated sheet. The chemical shifts of the diastereotopic hydrogens, that are bound to C-alpha, depend strongly on the positions of the carboxyl and carbamide moieties.
Keywords:C-13 SHIELDING TENSORS;LOCALIZED QUANTITIES;MAGNETIC-SUSCEPTIBILITIES;PERTURBATION-THEORY;SOLID-STATE;NMR;TERMS;ALPHA;CONFORMERS;MOLECULES