A new generation of effective core potentials from correlated calculations: 2nd row elements

摘要

Very recently, we have introduced correlation consistent effective core potentials (ccECPs) derived from many-body approaches with the main target being their use in explicitly correlated methods, while still usable in mainstream approaches. The ccECPs are based on reproducing excitation energies for a subset of valence states, namely, achieving near-isospectrality between the original and pseudo Hamiltonians. In addition, binding curves of dimer molecules were used for refinement and overall improvement of transferability over a range of bond lengths. Here we apply similar ideas to the 2nd row elements and study several aspects of the constructions in order to find the high accuracy solutions within the chosen ccECP forms with 3s, 3p valence space (Ne-core). Our new constructions exhibit accurate low-lying atomic excitations and equilibrium molecular bonds (on average within approximate to 0.03 eV and 3 m angstrom); however, the errors for Al and Si oxide molecules at short bond lengths are notably larger for both ours and existing effective core potentials. Assuming this limitation, our ccECPs show a systematic balance between the criteria of atomic spectra accuracy and transferability for molecular bonds. In order to provide another option with much higher uniform accuracy, we also construct He-core ccECPs for the whole 2nd row with typical discrepancies of approximate to 0.01 eV or smaller. Published by AIP Publishing.