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Relativistic quintuple-zeta basis sets for the p block

Marten L. Reitsma, Eifion H. Prinsen, Johan D. Polet, Anastasia Borschevsky, Kenneth G. Dyall

TL;DR

The authors address the need for high-accuracy relativistic basis sets for heavy p-block elements by developing and testing relativistic quintuple-zeta (5z) basis sets. They optimize SCF-occupied spinors under the Dirac-Coulomb Hamiltonian and derive valence/core correlating functions via multireference SDCI, supplemented by diffuse functions for anion-like states and outer-core polarization functions. The 5z p-block sets are validated through CBS extrapolations and calculations of bond lengths, dissociation energies, ionization potentials, and electron affinities, showing smooth convergence and measurable improvements over lower-zeta sets (on the order of a few mÅ for r_e and tens of meV for energies). The results demonstrate the practical impact of these basis sets for accurate heavy-element chemistry and provide access to the data on Zenodo for broad use with advanced relativistic methods.

Abstract

Relativistic quintuple-zeta basis sets for the p elements are presented. The basis sets for the occupied spinors were optimized at the Dirac-Coulomb self-consistent field (SCF) level on the ground configurations. Valence and core correlating functions were optimized in multireference SDCI calculations on the ground configuration. Diffuse functions optimized on the anion (or derived from neighboring elements for group 18) are also provided. Basic atomic and molecular properties were used to test the newly developed basis sets. A smooth convergence to the basis set limit is observed with increased basis set quality from the previously available double-zeta, triple-zeta, and quadruple-zeta basis sets to the newly developed quintuple-zeta basis sets for the calculated molecular bond lengths and dissociation energies and for atomic ionization potentials and electron affinities. Use of these basis sets in combination with state-of-the-art approaches for treatment of relativity and correlation will allow significantly increased accuracy in calculations on the heavy elements and their compounds. The basis sets are available at https://doi.org/10.5281/zenodo.18351835.

Relativistic quintuple-zeta basis sets for the p block

TL;DR

The authors address the need for high-accuracy relativistic basis sets for heavy p-block elements by developing and testing relativistic quintuple-zeta (5z) basis sets. They optimize SCF-occupied spinors under the Dirac-Coulomb Hamiltonian and derive valence/core correlating functions via multireference SDCI, supplemented by diffuse functions for anion-like states and outer-core polarization functions. The 5z p-block sets are validated through CBS extrapolations and calculations of bond lengths, dissociation energies, ionization potentials, and electron affinities, showing smooth convergence and measurable improvements over lower-zeta sets (on the order of a few mÅ for r_e and tens of meV for energies). The results demonstrate the practical impact of these basis sets for accurate heavy-element chemistry and provide access to the data on Zenodo for broad use with advanced relativistic methods.

Abstract

Relativistic quintuple-zeta basis sets for the p elements are presented. The basis sets for the occupied spinors were optimized at the Dirac-Coulomb self-consistent field (SCF) level on the ground configurations. Valence and core correlating functions were optimized in multireference SDCI calculations on the ground configuration. Diffuse functions optimized on the anion (or derived from neighboring elements for group 18) are also provided. Basic atomic and molecular properties were used to test the newly developed basis sets. A smooth convergence to the basis set limit is observed with increased basis set quality from the previously available double-zeta, triple-zeta, and quadruple-zeta basis sets to the newly developed quintuple-zeta basis sets for the calculated molecular bond lengths and dissociation energies and for atomic ionization potentials and electron affinities. Use of these basis sets in combination with state-of-the-art approaches for treatment of relativity and correlation will allow significantly increased accuracy in calculations on the heavy elements and their compounds. The basis sets are available at https://doi.org/10.5281/zenodo.18351835.
Paper Structure (11 sections, 2 equations, 5 figures, 10 tables)

This paper contains 11 sections, 2 equations, 5 figures, 10 tables.

Table of Contents

  1. Introduction
  2. Methods
  3. SCF sets
  4. Correlating sets
  5. Diffuse functions
  6. Outer core polarization functions
  7. Basis set results
  8. Applications
  9. Bond lengths and dissociation energies
  10. Ionization potentials and electron affinities
  11. Conclusions

Figures (5)

  • Figure 1: Bond length of PN using the CCSD and CCSD(T) methods as a function of basis set cardinality. Markers indicate the calculated values, and the CBS(4z) and CBS(5z) extrapolations are shown as dotted and solid lines, respectively.
  • Figure 2: Bond length of CLv using the CCSD and CCSD(T) methods as a function of basis set cardinality. Markers indicate the calculated values, and the CBS(4z) and CBS(5z) extrapolations are shown as dotted and solid lines, respectively.
  • Figure 3: Dissociation energy of CLv using the CCSD and CCSD(T) methods as a function of basis set cardinality. Markers indicate the calculated values, and the CBS(4z) and CBS(5z) extrapolations are shown as dotted and solid lines, respectively.
  • Figure 4: Total energies of Og and its ion (top panels) and IP (bottom panel) as a function of basis set cardinality, calculated with CCSD and CCSD(T). Markers indicate the calculated values, and the CBS(4z) and CBS(5z) extrapolations are shown as dotted and solid lines, respectively.
  • Figure 5: Total energies of Ts and its anion (top panels) and EA (bottom panel) as a function of basis set cardinality, calculated with CCSD and CCSD(T). Markers indicate the calculated values, and the CBS(4z) and CBS(5z) extrapolations are shown as dotted and solid lines, respectively.