The rotational spectrum of Roesky’s ketone

The experimental rotational spectrum of 5-oxo-1,3,2,4-dithiadiazole (Roesky’s ketone) has been recorded and the experimental rotational constants have been determined. The latter have been used to evaluate the performance of a large number of quantum chemical methods combined with different basis sets, by comparing the calculated with the experimental values. The results of this comparison indicate that, in general, the wave-function-based methods perform better than those from Density Functional Theory. Four of the 42 investigated method/basis set combinations prove to be the most valuable, i.e., MP4(SDQ)/(aug-)cc-pVTZ, B3PW91/cc-pV(T+d)Z and MPW1PW91/aug-cc-pVTZ, as they produce rotational constants with a root-mean-square deviation from the experimental values of only about 5 MHz.