Slimmer Geminals For Accurate F12 Electronic Structure Models
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arXiv
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| Auteurs principaux: | , , , |
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| Format: | Preprint |
| Publié: |
2025
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| _version_ | 1866918158118420480 |
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| author | Powell, Samuel R. Surjuse, Kshitijkumar A. Gaudel, Bimal Valeev, Edward F. |
| author_facet | Powell, Samuel R. Surjuse, Kshitijkumar A. Gaudel, Bimal Valeev, Edward F. |
| contents | The Slater-type F12 geminal lengthscales originally tuned for the second-order Møller-Plesset F12 method are too large for higher-order F12 methods formulated using the SP (diagonal fixed-coefficient spin-adapted) F12 ansatz. The new geminal parameters reported herein reduce the basis set incompleteness errors (BSIE) of absolute coupled-cluster singles and doubles F12 correlation energies by a significant - and increasing with the cardinal number of the basis - margin. The effect of geminal reoptimization is especially pronounced for the cc-pVXZ-F12 basis sets (specifically designed for use with F12 methods) relative to their conventional aug-cc-pVXZ counterparts. The BSIEs of relative energies are less affected but substantial reductions can be obtained, especially for atomization energies and ionization potentials with the cc-pVXZ-F12 basis sets. The new geminal parameters are therefore recommended for all applications of high-order F12 methods, such as the coupled-cluster F12 methods and the transcorrelated F12 methods. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2506_10780 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Slimmer Geminals For Accurate F12 Electronic Structure Models Powell, Samuel R. Surjuse, Kshitijkumar A. Gaudel, Bimal Valeev, Edward F. Chemical Physics The Slater-type F12 geminal lengthscales originally tuned for the second-order Møller-Plesset F12 method are too large for higher-order F12 methods formulated using the SP (diagonal fixed-coefficient spin-adapted) F12 ansatz. The new geminal parameters reported herein reduce the basis set incompleteness errors (BSIE) of absolute coupled-cluster singles and doubles F12 correlation energies by a significant - and increasing with the cardinal number of the basis - margin. The effect of geminal reoptimization is especially pronounced for the cc-pVXZ-F12 basis sets (specifically designed for use with F12 methods) relative to their conventional aug-cc-pVXZ counterparts. The BSIEs of relative energies are less affected but substantial reductions can be obtained, especially for atomization energies and ionization potentials with the cc-pVXZ-F12 basis sets. The new geminal parameters are therefore recommended for all applications of high-order F12 methods, such as the coupled-cluster F12 methods and the transcorrelated F12 methods. |
| title | Slimmer Geminals For Accurate F12 Electronic Structure Models |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2506.10780 |