From Wavefunction Sign Structure to Static Correlation
Fuente:
arXiv
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| Natura: | Preprint |
| Pubblicazione: |
2025
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| _version_ | 1866913063594098688 |
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| author | Dubecký, Matúš |
| author_facet | Dubecký, Matúš |
| contents | A variational nodal partition of the correlation energy is introduced, $E_{\mathrm{cor}}=E_{\mathrm{sym}}+E_{\mathrm{stat}}$, relative to a chosen mean-field correlation baseline and its associated single-determinant node. Static correlation $E_{\mathrm{stat}}$ is the negative of the energy penalty incurred when the many-electron wavefunction is constrained to that reference node rather than the exact one. This nodal term isolates the antisymmetric, sign-structure component of correlation, while the complementary symmetric term $E_{\mathrm{sym}}$ necessarily contains dynamic correlation together with a distinct strong but nodeless contribution. The resulting state-based, method-independent framework clarifies the relation between dynamic, nondynamic, strong, and static correlation, places earlier node-based decompositions on rigorous footing, and explains why single-determinant fixed-node diffusion Monte Carlo can be highly accurate in some systems yet fail in others. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2511_01569 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | From Wavefunction Sign Structure to Static Correlation Dubecký, Matúš Strongly Correlated Electrons Chemical Physics A variational nodal partition of the correlation energy is introduced, $E_{\mathrm{cor}}=E_{\mathrm{sym}}+E_{\mathrm{stat}}$, relative to a chosen mean-field correlation baseline and its associated single-determinant node. Static correlation $E_{\mathrm{stat}}$ is the negative of the energy penalty incurred when the many-electron wavefunction is constrained to that reference node rather than the exact one. This nodal term isolates the antisymmetric, sign-structure component of correlation, while the complementary symmetric term $E_{\mathrm{sym}}$ necessarily contains dynamic correlation together with a distinct strong but nodeless contribution. The resulting state-based, method-independent framework clarifies the relation between dynamic, nondynamic, strong, and static correlation, places earlier node-based decompositions on rigorous footing, and explains why single-determinant fixed-node diffusion Monte Carlo can be highly accurate in some systems yet fail in others. |
| title | From Wavefunction Sign Structure to Static Correlation |
| topic | Strongly Correlated Electrons Chemical Physics |
| url | https://arxiv.org/abs/2511.01569 |