The accuracy of rotational constants predicted by high-level quantum-chemical calculations. I. molecules containing first-row atoms

Abstract

A statistical analysis of the accuracy of theoretically predicted rotational constants is presented based on the data for a total of $16\text{molecules}$ and 97 isotopologues. Special focus is given on the treatment of electron correlation by using coupled-cluster methods up to quadruple excitations, core correlation, basis-set effects, zero-point vibrational corrections, and the electronic contribution to the rotational constants. The high accuracy achieved in the present investigation is demonstrated by the fact that at our best theoretical level, termed as $\mathrm{CCSD}\left(\mathrm{T}\right)∕\mathrm{cc}\text{-}\mathrm{pV}\infty \mathrm{Z}+\Delta \text{core}+\Delta T+\Delta Q+\Delta B_{\mathrm{vib}}+\Delta B_{\mathrm{el}}$ , the mean absolute error is 0.04% and the standard deviation is 0.07% in comparison with the available experimental data. The importance of higher excitations, core correlation, and zero-point vibrational effects is emphasized, while the electronic contribution is found to be less important.