Abstract
The selection of basis sets is very important for multiconfigurational wave function calculation, due to a balance between a desired accuracy and computational costs. Recently, the atomic natural orbital-relativistic (ANO-R) basis set was published as a suggested replacement for the ANO-RCC basis set for scalar-relativistic correlated calculations Zobel et al (2021 J. Chem. Theory Comput. 16 278–294). Benchmarking ANO-R basis set against ANO-RCC for atoms (from H to Rn) and their compounds is the goal of this study. Many of these compounds (for instance, diatomic molecules containing transition metals) have open shells, for which reason a multiconfigurational approach is necessary and was primarily used throughout this project. Performance of the ANO-R basis set in multiconfigurational calculations is similar to the ANO-RCC basis set for the ionisation potential of atoms, and the bond distance in diatomic molecules. Deficiencies are noted for atomic electron affinities and dissociation energies of fluoride diatomic molecules. ANO-R basis sets are more compact in comparison to the corresponding ANO-RCC basis sets leading to smaller computational costs, which was demonstrated by chloroiron corrole molecule as an example.
Highlights
Introduction ce an us criThe selection of a basis set is a key step in every Quantum Chemical calculation
Popular examples of atomic basis sets include Pople-type basis sets [4, 5], the Karlsruhe basis sets [6,7,8,9,10,11], Dyall basis sets [12,13,14], correlationconsistent basis sets [15,16,17,18,19,20,21,22], polarisation-consistent basis sets [23, 24], or basis sets based on atomic natural orbitals (ANO). [25, 26]
We have shown that the ANO-R basis set is able to achieve similar performance as its predecessor ANO-RCC in a wide range of test cases
Summary
Introduction ce an us criThe selection of a basis set is a key step in every Quantum Chemical calculation. The quality of the basis set influences the accuracy that can be achieved within a chosen method, but an increase of the basis set size leads to increase of the computational costs of the calculation. [10, 11, 13, 14, 20, 22, 27,28,29,30] These basis sets can be assigned to two different families that follow either a segmented [31] (Pople, Karlsruhe) or a general [32] contraction scheme (cc, pc, Dyall, ANO). While generallycontracted basis sets can, in principle, achieve a higher accuracy [33, 34], segmented basis sets allow for faster integral calculation, which can be an important part of the total computation time, especially when using low-scaling quantum-chemical methods
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