Relativistic adapted Gaussian basis sets free of variational prolapse of small and medium size for hydrogen through xenon

Abstract

Two new relativistic adapted Gaussian basis sets of small and medium size are presented for all elements from Hydrogen through Xenon. These sets are free of variational prolapse and were developed with the polynomial generator coordinate Dirac‐Fock method to be used with two finite nuclear models, uniform sphere and Gaussian. The largest basis set errors for electronic configurations from the Aufbau principle are around 10.0 and 4.7 mHartree for the small– and medium–size sets, respectively, which is in accordance with the accuracy level expected in each case. Hence, to our knowledge, these are the smallest prolapse free basis sets developed for these elements.

Relativistic adapted Gaussian basis sets free of variational prolapse of small and medium size for cesium through radon

“…As one could expect from the results achieved in our previous work for hydrogen until xenon, 12 the initially optimized sets show variational prolapse signals for all the atoms from Cs through Rn. This was confirmed by additional calculations done with extra tight functions generated by extrapolation of the polynomial expressions seen in Equations () and ().…”

“…The work initiated before 12 is continued here by developing two new RGBSs for the elements from Cesium to Radon, which are made free of variational prolapse and present small and medium sizes (MRPF and SRPF). To our knowledge, these are the smallest prolapse‐free RGBSs ever designed for these elements.…”

“…Following the previous basis set generation protocol, 12 the atomic Dirac–Fock‐Coulomb (DFC) calculations needed for developing basis sets are carried out by using the DFRATOM code 13 . The p‐GCDF parameters were optimized with the SIMPLEX 14 algorithm, which is guided by energy results from DFRATOM.…”

“…This was confirmed by additional calculations done with extra tight functions generated by extrapolation of the polynomial expressions seen in Equations () and (). Again, this deficiency can be successfully solved by the same procedure used before, 10–12 providing the definitive SRPF and MRPF sets of primitive functions, which are going to be complemented by polarization functions in future work.…”

“…Recently, we initiated this task by developing two new prolapse‐free RGBSs from hydrogen to xenon that present small and medium sizes (SRPFs and MRPFs, respectively) 12 . Here, we report the sequence of the efforts in that direction by addressing now the elements from cesium through radon.…”