English

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

Materials Science 2018-09-17 v2 Chemical Physics

Abstract

Very recently, we have introduced correlation consistent effective core potentials (ccECPs) derived from many-body approaches with the main target being its use in explicitly correlated methods but also in mainstream approaches. The ccECPs are based on reproducing excitation energies for a subset of valence states, i.e., achieving a near-isospectrality between the original and pseudo Hamiltonians. In addition, binding curves of dimer molecules have been used for refinement and overall improvement of transferability over a range of bond lengths. Here we apply similar ideas to the second row elements and study several aspects of the constructions in order to find the optimal (or nearly-optimal) solutions within the chosen ECP forms with 3s,3p3s,3p valence space (Ne-core). New constructions exhibit accurate low-lying atomic excitations and equilibrium molecular bonds (on average within \approx 0.030.03 eV and 33 m\AA), however, the errors for Al and Si oxide molecules at short bond lengths are notably larger for both ours and existing ECPs. 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 ECPs for the whole row with typical discrepancies of \approx 0.01 eV or smaller.

Keywords

Cite

@article{arxiv.1805.00607,
  title  = {New generation of effective core potentials from correlated calculations: 2nd row elements},
  author = {M. Chandler Bennett and Guangming Wang and Abdulgani Annaberdiyev and Cody A. Melton and Luke Shulenburger and Lubos Mitas},
  journal= {arXiv preprint arXiv:1805.00607},
  year   = {2018}
}
R2 v1 2026-06-23T01:42:18.831Z