Prediction of the aqueous redox properties of functionalized quinones using a new QM/MM variational formulation
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arXiv
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| Natura: | Preprint |
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2025
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| _version_ | 1866917094792101888 |
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| author | Labat, Maxime Jeanmairet, Guillaume Giner, Emmanuel |
| author_facet | Labat, Maxime Jeanmairet, Guillaume Giner, Emmanuel |
| contents | We recently proposed a method coupling quantum mechanics (QM) methods and molecular density functional theory (MDFT) to describe mixed quantum-classical systems [J. Chem. Phys. 161, 014113 (2024)]. This approach is particularly appropriate to account for solvent effect into QM calculations. We introduce a new variational formulation for the grand potential of a mixed quantum-classical system. Within the Born-Oppenheimer approximation and neglecting electronic entropy, the quantum solute is described by a product of electronic and nuclear density matrices, both depending parametrically on coordinates of the classical solvent. It can then be shown that a functional of the total density matrix satisfies a variational principle for the grand potential. Using a mean-field approximation, we express the grand potential of the mixed quantum-classical system as a variational problem which depends only on the nuclear density matrix, which experiences an external field generated by the electronic and classical one-particle densities. In practice, the grand potential is computed by a series of coupled classical and quantum DFT calculations, together with geometry optimization. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2506_12448 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Prediction of the aqueous redox properties of functionalized quinones using a new QM/MM variational formulation Labat, Maxime Jeanmairet, Guillaume Giner, Emmanuel Chemical Physics Soft Condensed Matter We recently proposed a method coupling quantum mechanics (QM) methods and molecular density functional theory (MDFT) to describe mixed quantum-classical systems [J. Chem. Phys. 161, 014113 (2024)]. This approach is particularly appropriate to account for solvent effect into QM calculations. We introduce a new variational formulation for the grand potential of a mixed quantum-classical system. Within the Born-Oppenheimer approximation and neglecting electronic entropy, the quantum solute is described by a product of electronic and nuclear density matrices, both depending parametrically on coordinates of the classical solvent. It can then be shown that a functional of the total density matrix satisfies a variational principle for the grand potential. Using a mean-field approximation, we express the grand potential of the mixed quantum-classical system as a variational problem which depends only on the nuclear density matrix, which experiences an external field generated by the electronic and classical one-particle densities. In practice, the grand potential is computed by a series of coupled classical and quantum DFT calculations, together with geometry optimization. |
| title | Prediction of the aqueous redox properties of functionalized quinones using a new QM/MM variational formulation |
| topic | Chemical Physics Soft Condensed Matter |
| url | https://arxiv.org/abs/2506.12448 |