On the basis set selection for molecular core-level $GW$ calculations

Abstract

The $GW$ approximation has been recently gaining popularity among the method for simulating molecular core-level X-ray photoemission spectra. Traditionally, $GW$ core-level binding energies have been computed using either the cc-pV$n$Z or def2-$n$ZVP basis set families, extrapolating the obtained results to the complete basis set limit, followed by a an element-specific relativistic correction. Despite of achieving good accuracy, these binding energies are chronically underestimated. By using first-row elements and standard techniques known to offer good cost-accuracy ratio in other theories, we show that the cc-pV$n$Z and def2-$n$ZVP families show large contraction errors and lead to unreliable complete basis set extrapolations. On the other hand, we demonstrate that uncontracted versions of these basis sets offer vastly improved convergence. Even faster convergence can be obtained using core-rich, property-optimized, basis sets families like pcSseg-$n$, pcJ-$n$ and ccX-$n$Z. Finally, we also show that the improvement over the core properties does not degrade the calculation of the valence excitations, and thus offer a balanced description of both core and valence regions.

References in corpus (4)

• NWChem: Past, Present, and Future
• Relativistic EOM-CCSD for core-excited and core-ionized state energies based on the 4-component Dirac-Coulomb(-Gaunt) Hamiltonian
• Scalable Molecular GW Calculations: Valence and Core Spectra
• Relativistic correction scheme for core-level binding energies from $GW$

Cited by in corpus (7)

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• Renormalized Singles with Correlation in $GW$ Green's Function Theory for Accurate Quasiparticle Energies
• Joint Approximate Diagonalization approach to Quasiparticle Self-Consistent $GW$ calculations
• $G_0{W}_0$ Ionization Potentials of First-Row Transition Metal Aqua Ions
• Enhancing the Accuracy of XPS Calculations: Exploring Hybrid Basis Set Schemes for CVS-EOMIP-CCSD Calculations
• Efficient $GW$ band structure calculations using Gaussian basis functions and application to atomically thin transition-metal dichalcogenides