Correlation-consistent Gaussian basis sets for copper solids from material-constrained atomic optimization
Abstract
Correlation-consistent Gaussian basis sets are central to systematic molecular quantum chemistry, but their direct use in periodic solids is often limited by severe linear dependence from diffuse atomically optimized primitives. This problem is particularly acute for metallic and metal-containing systems, where reliable complete-basis-set (CBS) extrapolation is needed for correlated-wavefunction benchmarks. We introduce material-constrained atomic optimization (MCAO), a basis-set optimization framework that preserves the atomic and correlation-consistent character of Gaussian basis sets while penalizing large overlap-matrix condition numbers in representative solids. As a proof of concept, we generate Dunning-style MCAO-cc-pVXZ basis sets (X = D, T, Q) for Cu with all-electron, scalar-relativistic all-electron, effective core potential (ECP), and pseudopotential treatments. The resulting basis sets remain numerically stable for Cu solids and surfaces while reproducing molecular Cu dimer energetics and plane-wave reference properties of bulk Cu. CBS-extrapolated random-phase approximation calculations further enable a controlled assessment of pseudopotential, relativistic, and basis-set errors in bulk Cu and CO adsorption on Cu(111), providing scalar-relativistic all-electron Gaussian-basis benchmarks for the CO adsorption puzzle.
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BibTeX
@misc{yu2026correlationconsistent,
title = {{Correlation-consistent Gaussian basis sets for copper solids from material-constrained atomic optimization}},
author = {Jincheng Yu and Xiaoyu Zhang and Min-Ye Zhang and Yu Cao and Qiming Sun and Hong-Zhou Ye},
howpublished = {arXiv},
year = {2026},
month = nov,
doi = {10.48550/arxiv.2607.11711},
eprint = {2607.11711},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2607.11711},
note = {CC BY 4.0},
}
RIS
TY - UNPB
TI - Correlation-consistent Gaussian basis sets for copper solids from material-constrained atomic optimization
AU - Jincheng Yu
AU - Xiaoyu Zhang
AU - Min-Ye Zhang
AU - Yu Cao
AU - Qiming Sun
AU - Hong-Zhou Ye
PY - 2026
DA - 2026/11/04
PB - arXiv
DO - 10.48550/arxiv.2607.11711
UR - https://arxiv.org/abs/2607.11711
AB - Correlation-consistent Gaussian basis sets are central to systematic molecular quantum chemistry, but their direct use in periodic solids is often limited by severe linear dependence from diffuse atomically optimized primitives. This problem is particularly acute for metallic and metal-containing systems, where reliable complete-basis-set (CBS) extrapolation is needed for correlated-wavefunction benchmarks. We introduce material-constrained atomic optimization (MCAO), a basis-set optimization framework that preserves the atomic and correlation-consistent character of Gaussian basis sets while penalizing large overlap-matrix condition numbers in representative solids. As a proof of concept, we generate Dunning-style MCAO-cc-pVXZ basis sets (X = D, T, Q) for Cu with all-electron, scalar-relativistic all-electron, effective core potential (ECP), and pseudopotential treatments. The resulting basis sets remain numerically stable for Cu solids and surfaces while reproducing molecular Cu dimer energetics and plane-wave reference properties of bulk Cu. CBS-extrapolated random-phase approximation calculations further enable a controlled assessment of pseudopotential, relativistic, and basis-set errors in bulk Cu and CO adsorption on Cu(111), providing scalar-relativistic all-electron Gaussian-basis benchmarks for the CO adsorption puzzle.
ER -