Optimized Basis Sets for Calculation of Electron Paramagnetic Resonance Hyperfine Coupling Constants: aug-cc-pVTZ-J for the 3d Atoms Sc-Zn.

Abstract

The hyperfine coupling tensor of electron paramagnetic resonance (EPR), describing the interaction between an electron and a given nuclei, depends strongly on the electron density at the nucleus. With standard Gaussian-type orbital basis sets (GTOs), employed in most calculations, it is difficult to obtain converged results of the hyperfine coupling tensor, and basis sets with more flexible core regions have therefore been devised. To this class of core property basis sets belong the aug-cc-pVTZ-J basis sets developed for the s- and p-block atoms. Here, we extend the aug-cc-pVTZ-J basis sets to include the 3d elements Sc-Zn. The converged optimal basis sets are throughout the series described by a (25s17p10d3f2g)/[17s10p7d3f2g] contraction scheme, where four tight s-, one tight p-, and one tight d-type function have been added to the original aug-cc-pVTZ basis sets. The basis sets are generally contracted, and molecular orbital coefficients are used as contraction coefficients. By validation studies with different functionals and compounds, it is shown that the values of the contraction coefficient are effectively independent of the compound used in their generation and the exchange-correlation functional employed in the calculation.