Exploiting Non-Abelian Point-Group Symmetry to Estimate the Exact Ground-State Correlation Energy of Benzene in a Polarized Split-Valence Triple-Zeta Basis Set
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arXiv
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| Format: | Preprint |
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2024
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| _version_ | 1866909275037630464 |
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| author | Greiner, Jonas Gauss, Jürgen Eriksen, Janus J. |
| author_facet | Greiner, Jonas Gauss, Jürgen Eriksen, Janus J. |
| contents | Local electronic-structure methods in quantum chemistry operate on the ability to compress electron correlations more efficiently in a basis of spatially localized molecular orbitals than in a parent set of canonical orbitals. However, many typical choices of localized orbitals tend to be related by selected, near-exact symmetry operations whenever a molecule belongs to a point group, a feature which remains largely unexploited in most local correlation methods. The present Letter demonstrates how to leverage a recent unitary protocol for enforcing symmetry properties among localized orbitals to yield a high-accuracy estimate of the exact ground-state correlation energy of benzene ($D_{6h}$) in correlation-consistent polarized basis sets of both double- and triple-$ζ$ quality. Through an initial application to many-body expanded full configuration interaction (MBE-FCI) theory, we show how molecular point-group symmetry can lead to computational savings that are inversely proportional to the order of the point group in a manner generally applicable to the acceleration of modern local correlation methods. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2407_21576 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Exploiting Non-Abelian Point-Group Symmetry to Estimate the Exact Ground-State Correlation Energy of Benzene in a Polarized Split-Valence Triple-Zeta Basis Set Greiner, Jonas Gauss, Jürgen Eriksen, Janus J. Chemical Physics Local electronic-structure methods in quantum chemistry operate on the ability to compress electron correlations more efficiently in a basis of spatially localized molecular orbitals than in a parent set of canonical orbitals. However, many typical choices of localized orbitals tend to be related by selected, near-exact symmetry operations whenever a molecule belongs to a point group, a feature which remains largely unexploited in most local correlation methods. The present Letter demonstrates how to leverage a recent unitary protocol for enforcing symmetry properties among localized orbitals to yield a high-accuracy estimate of the exact ground-state correlation energy of benzene ($D_{6h}$) in correlation-consistent polarized basis sets of both double- and triple-$ζ$ quality. Through an initial application to many-body expanded full configuration interaction (MBE-FCI) theory, we show how molecular point-group symmetry can lead to computational savings that are inversely proportional to the order of the point group in a manner generally applicable to the acceleration of modern local correlation methods. |
| title | Exploiting Non-Abelian Point-Group Symmetry to Estimate the Exact Ground-State Correlation Energy of Benzene in a Polarized Split-Valence Triple-Zeta Basis Set |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2407.21576 |