RotGT-2023: A Benchmark Data Set of Rotational g Tensors

21 August 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


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 litera- ture 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 275 parameters from 127 molecules, including their isotopologues. Statistical assessment of the data has been performed to exclude unreliable pa- rameters. 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 1.19 % and 2.19 % 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) = 1.4733230(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.


Rotational g tensor
Molecular Zeeman effect
Molecular structure

Supplementary materials

Supplementary material
Details on computational procedures and molecular structure refinement are provided in supplementary material. Input and output files of the UNEX program, used for the refinement of molecular structure of SiH4 are also provided.


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