New generation of effective core potentials from correlated calculations: 3d transition metal series

TL;DR

This paper introduces a new set of effective core potentials for 3d transition metals, achieving high accuracy in correlated calculations and transferability across molecular systems.

Contribution

The paper presents a new generation of ECPs for 3d transition metals with improved accuracy and simplicity, based on correlated calculations and isospectrality principles.

Findings

High spectral accuracy with discrepancies around 0.01-0.02 eV.

Reproduces molecular binding curves within 0.02-0.03 eV.

Operators are simple, bounded, and represented by few Gaussians.

Abstract

Recently, we have introduced a new generation of effective core potentials (ECPs) designed for accurate correlated calculations but equally useful for a broad variety of approaches. The guiding principle has been the isospectrality of all-electron and ECP Hamiltonians for a subset of valence many-body states using correlated, nearly-exact calculations. Here we present such ECPs for the 3d transition series Sc to Zn with Ne-core, i.e, with semi-core 3s and 3p electrons in the valence space. Besides genuine many-body accuracy, the operators are simple, being represented by a few gaussians per symmetry channel with resulting potentials that are bounded everywhere. The transferability is checked on selected molecular systems over a range of geometries. The ECPs show a high overall accuracy with valence spectral discrepancies typically $\approx$ 0.01-0.02 eV or better. They also reproduce binding curves of hydride and oxide molecules typically within 0.02-0.03 eV deviations over the full non-dissociation range of interatomic distances.