Symmetrized non-decomposable approximations of the non-additive kinetic energy functional

Article Article scientifique Article Symmetrized non-decomposable approximations of the non-additive kinetic energy functional eng 2023-05-02 2023-05-07 author Polak Elias 0000-0001-5807-7631 853826 author Englert Tanguy 0009-0006-2875-8130 833506 Chimie physique (groupe 5) (CHIF5) author Gander Martin Jakob 0000-0001-8450-9223 134664 Section de mathématiques (MATH) author Wesolowski Tomasz Adam 0000-0001-5792-4616 92358 Département de chimie physique (CHIFI) 1-10 174107 10.1063/5.0143602 37129139 0021-9606 https://pubs.aip.org/jcp/article/158/17/174107/2887765/Symmetrized-non-decomposable-approximations-of-the <p>In subsystem density functional theory (DFT), the bottom-up strategy to approximate the multivariable functional of the non-additive kinetic energy (NAKE) makes it possible to impose exact properties on the corresponding NAKE potential (NAKEP). Such a construction might lead to a non-symmetric and non-homogeneous functional, which excludes the use of such approximations for the evaluation of the total energy. We propose a general formalism to construct a symmetric version based on a perturbation theory approach of the energy expression for the asymmetric part. This strategy is then applied to construct a symmetrized NAKE corresponding to the NAKEP developed recently [Polak et al., J. Chem. Phys. 156, 044103 (2022)], making it possible to evaluate consistently the energy. These functionals were used to evaluate the interaction energy in several model intermolecular complexes using the formal framework of subsystem DFT. The new symmetrized energy expression shows a superior qualitative performance over common decomposable models.</p> Dewey 540 Dewey 510 38 Département de chimie physique 142 25 Section de mathématiques 11 false The Journal of chemical physics 158 17 b467a343-b709-4ef2-9c7c-4a0ecbf44e2e Article (Published version) Public Polak_JCP_158.pdf 4842469 application/pdf CC BY-4.0 3be102621781945aa14b104ae9d37b407685cc875cbc86359233ac9825beda5e openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie physique Faculté des sciences / Section de mathématiques

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Symmetrized non-decomposable approximations of the non-additive kinetic energy functional	The Journal of chemical physics			2023	50	38

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Englert, Tanguy