FDE-vdW

A van der Waals inclusive subsystem density-functional theory

Ruslan Kevorkyants, Hendrik Eshuis, Michele Pavanello

Research output: Contribution to journalArticleResearchpeer-review

15 Citations (Scopus)

Abstract

We present a formally exact van der Waals inclusive electronic structure theory, called FDE-vdW, based on the Frozen Density Embedding formulation of subsystem Density-Functional Theory. In subsystem DFT, the energy functional is composed of subsystem additive and non-additive terms. We show that an appropriate definition of the long-range correlation energy is given by the value of the non-additive correlation functional. This functional is evaluated using the fluctuation-dissipation theorem aided by a formally exact decomposition of the response functions into subsystem contributions. FDE-vdW is derived in detail and several approximate schemes are proposed, which lead to practical implementations of the method. We show that FDE-vdW is Casimir-Polder consistent, i.e., it reduces to the generalized Casimir-Polder formula for asymptotic inter-subsystems separations. Pilot calculations of binding energies of 13 weakly bound complexes singled out from the S22 set show a dramatic improvement upon semilocal subsystem DFT, provided that an appropriate exchange functional is employed. The convergence of FDE-vdW with basis set size is discussed, as well as its dependence on the choice of associated density functional approximant.

Original languageEnglish
Article number044127
JournalJournal of Chemical Physics
Volume141
Issue number4
DOIs
StatePublished - 28 Jul 2014

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Discrete Fourier transforms
Density functional theory
density functional theory
Binding energy
embedding
Electronic structure
dissipation
theorems
binding energy
electronic structure
Decomposition
decomposition
formulations
energy

Cite this

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title = "FDE-vdW: A van der Waals inclusive subsystem density-functional theory",
abstract = "We present a formally exact van der Waals inclusive electronic structure theory, called FDE-vdW, based on the Frozen Density Embedding formulation of subsystem Density-Functional Theory. In subsystem DFT, the energy functional is composed of subsystem additive and non-additive terms. We show that an appropriate definition of the long-range correlation energy is given by the value of the non-additive correlation functional. This functional is evaluated using the fluctuation-dissipation theorem aided by a formally exact decomposition of the response functions into subsystem contributions. FDE-vdW is derived in detail and several approximate schemes are proposed, which lead to practical implementations of the method. We show that FDE-vdW is Casimir-Polder consistent, i.e., it reduces to the generalized Casimir-Polder formula for asymptotic inter-subsystems separations. Pilot calculations of binding energies of 13 weakly bound complexes singled out from the S22 set show a dramatic improvement upon semilocal subsystem DFT, provided that an appropriate exchange functional is employed. The convergence of FDE-vdW with basis set size is discussed, as well as its dependence on the choice of associated density functional approximant.",
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FDE-vdW : A van der Waals inclusive subsystem density-functional theory. / Kevorkyants, Ruslan; Eshuis, Hendrik; Pavanello, Michele.

In: Journal of Chemical Physics, Vol. 141, No. 4, 044127, 28.07.2014.

Research output: Contribution to journalArticleResearchpeer-review

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AU - Kevorkyants, Ruslan

AU - Eshuis, Hendrik

AU - Pavanello, Michele

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