Atomic forces from correlation energy functionals based on the adiabatic-connection fluctuation-dissipation theorem
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arXiv
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| Autores principales: | , |
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| Formato: | Preprint |
| Publicado: |
2025
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| _version_ | 1866918395678556160 |
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| author | Contant, Damian Hellgren, Maria |
| author_facet | Contant, Damian Hellgren, Maria |
| contents | We extend the capabilities of correlation energy functionals based on the adiabatic-connection fluctuation-dissipation theorem by implementing the analytical atomic forces within the random phase approximation (RPA), in the context of plane waves and pseudopotentials. Forces are calculated at self-consistency through the optimized effective potential method and the Hellmann-Feynman theorem. In addition, non-self-consistent RPA forces, starting from the PBE generalized gradient approximation, are evaluated using density functional perturbation theory. In both cases, we find forces of excellent numerical quality. Furthermore, for most molecules and solids studied, self-consistency is found to have a negligible impact on the computed geometries and vibrational frequencies. The RPA is shown to systematically improve over PBE and, by including the exact-exchange kernel within RPA + exchange (RPAx), through finite-difference total energy calculations, we obtain an accuracy comparable to advanced wavefunction methods. Finally, we estimate the anharmonic shift and provide accurate theoretical references based on RPA and RPAx for the zone-center optical phonon of diamond, silicon, and germanium. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2512_16460 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Atomic forces from correlation energy functionals based on the adiabatic-connection fluctuation-dissipation theorem Contant, Damian Hellgren, Maria Materials Science Chemical Physics Computational Physics We extend the capabilities of correlation energy functionals based on the adiabatic-connection fluctuation-dissipation theorem by implementing the analytical atomic forces within the random phase approximation (RPA), in the context of plane waves and pseudopotentials. Forces are calculated at self-consistency through the optimized effective potential method and the Hellmann-Feynman theorem. In addition, non-self-consistent RPA forces, starting from the PBE generalized gradient approximation, are evaluated using density functional perturbation theory. In both cases, we find forces of excellent numerical quality. Furthermore, for most molecules and solids studied, self-consistency is found to have a negligible impact on the computed geometries and vibrational frequencies. The RPA is shown to systematically improve over PBE and, by including the exact-exchange kernel within RPA + exchange (RPAx), through finite-difference total energy calculations, we obtain an accuracy comparable to advanced wavefunction methods. Finally, we estimate the anharmonic shift and provide accurate theoretical references based on RPA and RPAx for the zone-center optical phonon of diamond, silicon, and germanium. |
| title | Atomic forces from correlation energy functionals based on the adiabatic-connection fluctuation-dissipation theorem |
| topic | Materials Science Chemical Physics Computational Physics |
| url | https://arxiv.org/abs/2512.16460 |