Reference-Density Hartree Screening for Gausslet Hamiltonians

Abstract

Gausslets are among the few electronic-structure bases that permit the four-index electron--electron interaction to be replaced by an accurate two-index integral diagonal approximation (IDA). Near a many-electron nucleus, however, the nuclear attraction and core-electron Hartree field are individually large and substantially cancel. Treating the first as a full finite-basis matrix while treating the second with IDA leaves an avoidable imbalance. We introduce reference-density Hartree screening: the Hartree field of a chosen reference density is represented accurately, and IDA is applied only to density fluctuations about it. Tests on He, Ne, atomic F, F$_2$, and Cr$_2$ show large reductions in direct Hartree errors, including transfer of fitted neutral-atom fields to molecules. For Cr$_2$, atomic-core screening prevents the spurious HF collapse found with the unscreened $q=5$ and $q=7$ Hamiltonians, whereas finite-reference matching without screening does not. Screening leaves exchange and residual correlation unchanged. We therefore also introduce a low-rank one-particle correction that uses an accurate conventional Gaussian-basis Hartree--Fock calculation to match either occupied-space exchange information or the complete occupied Fock vectors. In F$_2$ and Cr$_2$, $X_{\rm HF}$ reproduces the finite-reference energy and occupied Fock vectors to numerical precision and the selected states return after orbital perturbations. For Cr$_2$, the corrected $q=5$ basis uses one quarter as many functions as the $q=7$ control while retaining sub-mHa mean-field accuracy. Screening provides the physical improvement to the direct field; the state-specific correction then restores the remaining accuracy of the Gaussian-basis mean-field reference.