Rovibrationally averaged nuclear shielding constants in OCS.

The nuclear shielding constants in OCS are studied using ab initio theoretical methods and gas-phase NMR measurements. The shielding surfaces are calculated and the rovibrational effects and the resulting temperature dependence are analyzed. The temperature dependence of 13C shielding in the gas phase is determined experimentally in the range 278-373 K. 13C is the single nucleus for which the experimental data for the temperature dependence can be converted to a reference-independent scale, and good agreement of the measured and calculated ab initio results is observed. For 33S, we discuss a new, more accurate absolute shielding scale.