Relativistic heavy atom effect on 13 C NMR chemical shifts initiated by adjacent multiple chalcogens.

Abstract

In this paper, we have investigated the cumulative peculiarity of the "heavy atom on light atom" effect on the 13 C NMR chemical shifts, initiated by the adjacent chalcogens. For this purpose, the most accurate hybrid computational scheme for the calculation of chemical shifts of carbon nuclei, directly bonded with several heavy chalcogens, is introduced and attested on the representative series of molecules. The best hybrid scheme combines the nonrelativistic coupled cluster-based approach with the different types of corrections, including vibrational, solvent, and relativistic. The dependences of the total relativistic corrections to carbon shielding constants in 2 series of model compounds, namely, X═13 C═Y (X, Y=O, S, Se, Te) and C(XH)m (YH)n (ZH)p (QH)s H1-m H1-n H1-p H1-s (X, Y, Z, Q=S, Se, Te and m, n, p, s=0, 1), on the total atomic number of the adjacent chalcogens have been obtained.