Encoding electronic ground-state information with variational even-tempered basis sets
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arXiv
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| Autores principales: | , , |
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| Formato: | Preprint |
| Publicado: |
2025
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| _version_ | 1866910027545051136 |
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| author | Wang, Weishi Dowdle, Casey Whitfield, James D. |
| author_facet | Wang, Weishi Dowdle, Casey Whitfield, James D. |
| contents | We propose a system-oriented basis-set design based on even-tempered basis functions to variationally encode electronic ground-state information into molecular orbitals. First, we introduce a reduced formalism of concentric even-tempered orbitals that achieves hydrogen energy accuracy on par with the conventional formalism, with lower optimization cost and improved scalability. Second, we propose a symmetry-adapted, even-tempered formalism specifically designed for molecular systems. It requires only primitive S-subshell Gaussian-type orbitals and uses two parameters to characterize all exponent coefficients. In the case of the diatomic hydrogen molecule, the basis set generated by this formalism produces a dissociation curve more consistent with cc-pV5Z than cc-pVTZ at the size of aug-cc-pVDZ. Finally, we test our even-tempered formalism against several types of tetra-atomic hydrogen molecules for ground-state computation and point out its current limitations and potential improvements. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2511_03579 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Encoding electronic ground-state information with variational even-tempered basis sets Wang, Weishi Dowdle, Casey Whitfield, James D. Chemical Physics Strongly Correlated Electrons Atomic Physics Computational Physics Quantum Physics We propose a system-oriented basis-set design based on even-tempered basis functions to variationally encode electronic ground-state information into molecular orbitals. First, we introduce a reduced formalism of concentric even-tempered orbitals that achieves hydrogen energy accuracy on par with the conventional formalism, with lower optimization cost and improved scalability. Second, we propose a symmetry-adapted, even-tempered formalism specifically designed for molecular systems. It requires only primitive S-subshell Gaussian-type orbitals and uses two parameters to characterize all exponent coefficients. In the case of the diatomic hydrogen molecule, the basis set generated by this formalism produces a dissociation curve more consistent with cc-pV5Z than cc-pVTZ at the size of aug-cc-pVDZ. Finally, we test our even-tempered formalism against several types of tetra-atomic hydrogen molecules for ground-state computation and point out its current limitations and potential improvements. |
| title | Encoding electronic ground-state information with variational even-tempered basis sets |
| topic | Chemical Physics Strongly Correlated Electrons Atomic Physics Computational Physics Quantum Physics |
| url | https://arxiv.org/abs/2511.03579 |