Strategy for constructing compact numerical atomic orbital basis sets by incorporating the gradients of reference wavefunctions

Abstract

We develop an algorithm to construct high-quality numerical atomic orbital (NAO) basis sets suitable for large-scale, efficient density-functional calculations. The key idea behind this algorithm is that, in addition to fitting the reference wavefunctions themselves generated by plane-wave based calculations of chosen target systems, the first derivatives of the reference wavefunctions are also taken into account as the fitting target. By doing so, the quality of the generated NAO basis sets is significantly improved in the sense that the same level of numerical precision can be achieved with smaller basis set sizes or with reduced cutoff radii of the NAOs.