RotGT-2023: A benchmark data set of rotational g tensors

Abstract

The largest ever set, RotGT-2023, of statistically validated experimental components of rotational g tensors and respective vibrational corrections, has been created. The experimental values were collected from literature data. The vibrational corrections for obtaining equilibrium molecular g values have been calculated at the highest affordable coupled cluster level of theory. The set comprises 278 parameters from 129 molecules, including their isotopologues. Statistical assessment of the data has been performed to exclude unreliable parameters. A benchmarking of two theoretical approximations, based on coupled cluster and density functional theories, has been performed. The determined weighted mean and weighted standard deviations of the relative errors in calculated equilibrium g values are 1.09% and 2.07% for the ae-CCSD(T)/x2c-TZVPPall-s//ae-CCSD(T)/cc-pwCVTZ level. The obtained results can be used for predicting the rotational Zeeman effect, correcting rotational constants in spectroscopic studies and in molecular structure refinements. The latter has been demonstrated on the refinement of the molecular structure of silane SiH4, which resulted in rese(Si–H) = 1.473 323 1(27) Å. The other tested theoretical protocol, PBE0/x2c-TZVPPall-s//PBE0-D3BJ/def2-QZVPP, showed considerably worse statistical properties. The RotGT-2023 data set and the developed in this work statistical model are recommended for benchmarking of theoretical approximations for calculations of molecular magnetic properties.