Basis Set Superposition Errors Are Partly Basis Set Imbalances

2024/01/04 by Frank Jensen · 1 voice
Materials Science · Physics and Astronomy · #Machine Learning in Materials Science #Advanced Chemical Physics Studies #X-ray Diffraction in Crystallography

paper · doi:10.1021/acs.jctc.3c01156

openalex publication_date 2024/01/04 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/08

Abstract

When calculating fragment interaction energies by electronic structure methods employing medium-sized atom-centered basis sets, it is often observed that the effect is systematically overestimated. The common interpretation is that the systematic error arises because the basis set for the complex is more complete than for the isolated fragments, and this is denoted basis set superposition errors. It has been observed, however, that the interaction energy in some cases is underestimated, which defies the interpretation in terms of basis set completeness, and instead suggests that the effect partly is due to basis set imbalance. The imbalance can be removed by explicit optimization of the basis sets for each structure, and it is shown that this to a significant extent reduces the systematic overestimation attributed to basis set superposition error.

Citations

• Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
• The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors
• Chemistry with ADF

Discussions

• #compchem Good read: Basis Set Superposition Errors Are Partly Basis Set Imbalances doi.org/10.1021/acs.... [bsky, 2 points, 0 comments]

Related

• A complete basis set model chemistry. III. The complete basis set-quadratic configuration interaction family of methods
• Correcting basis set incompleteness in wave function correlation energy by dressing electronic Hamiltonian with an effective short-range interaction
• Basis set incompleteness errors in fixed-node diffusion Monte Carlo calculations on non-covalent interactions
• The Conundrum of Diffuse Basis Sets: A Blessing for Accuracy yet a Curse for Sparsity
• Predicting complete basis set limit quasiparticle energies from triple-ζ calculations