Replication Data for: Static polarizabilities at the basis set limit: A benchmark of 124 species

Abstract

Introduction This Dataverse entry contains replication data for our journal article “Static polarizabilities at the basis set limit: A benchmark of 124 species” published in Journal of Chemical Theory and Computation. It contains highly precise static polarizabilities computed in multiwavelet basis in combination with density functional theory (DFT, PBE functional). In addition, the d/Preliminaryata set contains analysis tools (Jupyter Notebooks with Python3 code) for generating the figures in the journal article. How to use Because our multiwavelet data is guaranteed to be at the complete basis set limit (to within the specified limit), it is suitable as a benchmark reference in studies of static polarizabilities where the basis set convergence is important. With multiwavelets we don't have to assume that the computed property is at the basis set limit, as is the case with Gaussian type orbital (GTO) basis sets, and it is therefore possible to confirm whether the property of interest computed basis is sufficiently converged with respect to the complete basis set limit. Our benchmark reference can also be used in the development of new methodology that requires accurate training data. Running the Jupyter Notebooks The Anaconda Python distribution is usually recommended for obtaining Jupyter Notebook. It can be downloaded from here: https://www.anaconda.com/distribution/ Note that the file functions.py and the relevant DataSet files have to be located in the same directory as the notebook you are trying to run, in order for the code to run without errors. Journal article Submitted for review... (Preliminary) Abstract from journal article Benchmarking molecular properties with Gaussian-type orbital (GTO) basis sets can be challenging, because one has to assume that the computed property is at the complete basis set (CBS) limit. However, multiwavelet (MW) bases are inherently at the CBS limit, which eliminates the need for such assumptions. In this work, we have used MWs within Kohn–Sham (KS)–density functional theory (DFT) to compute static polarizabilities for a set of 92 closed-shell and 32 open-shell species. The results are compared to recent benchmark calculations employing the GTO-type aug-pc4 basis set. We observe discrepancies between GTO and MW results for several species, with open- shell systems showing the largest deviations. Based on linear response calculations, we show that these discrepancies originate from artefacts caused by the field strength, which negatively impact finite-difference GTO polarizabilities, but not finite-difference MW ones. Based on our MW benchmark results, we can affirm that aug-pc4 is able to provide results close to the CBS limit, as long as finite-difference effects can be controlled. However, we suggest that a better approach is to use MWs, which are able to yield precise finite-difference polarizabilities even with small field strengths.