Improved Basis-Set Incompleteness Potentials for Accurate Density-Functional Theory Calculations in Large Systems
Bibliographic record
Abstract
The accurate calculation of chemical properties using density-functional theory (DFT) requires the use of a nearly complete basis set. In chemical systems involving hundreds to thousands of atoms, the cost of the calculations place practical limitations on the number of basis functions that can be used. Therefore, in most practical applications of DFT to large systems, there exists a basis-set incompleteness error (BSIE). In this article, we present the next iteration of the basis-set incompleteness potentials (BSIPs), one-electron potentials designed to correct for basis-set incompleteness error. The ultimate goal associated with the development of BSIPs is to allow the calculation of molecular properties using DFT with near-complete-basis-set results at a computational cost that is similar to a small basis set calculation. In this work, we develop BSIPs for 10 atoms in the first and second rows (H, B-F, Si-Cl) and 15 common basis sets of the Pople, Dunning, Karlsruhe, and Huzinaga types. Our new BSIPs are constructed to minimize BSIE in the calculation of reaction energies, barrier heights, noncovalent binding energies, and intermolecular distances. The BSIPs were obtained using a training set of 15 944 data points. The fitting approach employed a regularized linear least-squares method with variable selection (the LASSO method), which results in a much better fit to the training data than our previous BSIPs while, at the same time, reducing the computational cost of BSIP development. The proposed BSIPs are tested on various benchmark sets and demonstrate excellent performance in practice. Our new BSIPs are also transferable; i.e., they can be used to correct BSIE in calculations that employ density functionals other than the one used in the BSIP development (B3LYP). Finally, BSIPs can be used in any quantum chemistry program that have implemented effective-core potentials without changes to the software.
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.004 | 0.009 |
| Meta-epidemiology (narrow) | 0.001 | 0.001 |
| Meta-epidemiology (broad) | 0.001 | 0.001 |
| Bibliometrics | 0.001 | 0.001 |
| Science and technology studies | 0.001 | 0.001 |
| Scholarly communication | 0.001 | 0.001 |
| Open science | 0.002 | 0.002 |
| Research integrity | 0.001 | 0.002 |
| Insufficient payload (model declined to judge) | 0.002 | 0.001 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".