Correcting DFT errors through v-representable density partitioning

Piotr de Silva, Tianyu Zhu, Troy Van Voorhis

Research output: Contribution to journalConference abstract in journalResearchpeer-review

Abstract

The recently introduced Self-Attractive Hartree (SAH) decomposition is a method to partition electron density into smooth localized fragments. The fragment densities are obtained through a regularized maximization of self-repulsion. The resulting set of eigenvalue equations resembles Kohn-Sham equations for electrons experiencing self-attractive Hartree potential and external potential common for all fragments. Ground-state solutions of these equations are by construction v-representable and effectively visualize bonding patterns in molecular systems.
We show how these smooth density fragments can be used to correct errors of approximate density functionals like self-interaction or missing van der Waals interactions. To this end we introduce the many-pair expansion (MPE), which is a systematically improvable correction scheme converging to the exact energy. Possible applications in density embedding approaches and orbital-free DFT are also discussed.
Original languageEnglish
JournalAmerican Chemical Society. Abstracts of Papers (at the National Meeting)
Volume256
Number of pages1
ISSN0065-7727
Publication statusPublished - 2019
Event256th ASC National Meeting - Boston Convention & Exhibition Center, Boston, United States
Duration: 19 Aug 201823 Aug 2018

Conference

Conference256th ASC National Meeting
LocationBoston Convention & Exhibition Center
CountryUnited States
CityBoston
Period19/08/201823/08/2018

Bibliographical note

Program area: Division of Computers in Chemistry, COMP 14

Cite this

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title = "Correcting DFT errors through v-representable density partitioning",
abstract = "The recently introduced Self-Attractive Hartree (SAH) decomposition is a method to partition electron density into smooth localized fragments. The fragment densities are obtained through a regularized maximization of self-repulsion. The resulting set of eigenvalue equations resembles Kohn-Sham equations for electrons experiencing self-attractive Hartree potential and external potential common for all fragments. Ground-state solutions of these equations are by construction v-representable and effectively visualize bonding patterns in molecular systems.We show how these smooth density fragments can be used to correct errors of approximate density functionals like self-interaction or missing van der Waals interactions. To this end we introduce the many-pair expansion (MPE), which is a systematically improvable correction scheme converging to the exact energy. Possible applications in density embedding approaches and orbital-free DFT are also discussed.",
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Correcting DFT errors through v-representable density partitioning. / de Silva, Piotr; Zhu, Tianyu ; Voorhis, Troy Van.

In: American Chemical Society. Abstracts of Papers (at the National Meeting), Vol. 256, 2019.

Research output: Contribution to journalConference abstract in journalResearchpeer-review

TY - ABST

T1 - Correcting DFT errors through v-representable density partitioning

AU - de Silva, Piotr

AU - Zhu, Tianyu

AU - Voorhis, Troy Van

N1 - Program area: Division of Computers in Chemistry, COMP 14

PY - 2019

Y1 - 2019

N2 - The recently introduced Self-Attractive Hartree (SAH) decomposition is a method to partition electron density into smooth localized fragments. The fragment densities are obtained through a regularized maximization of self-repulsion. The resulting set of eigenvalue equations resembles Kohn-Sham equations for electrons experiencing self-attractive Hartree potential and external potential common for all fragments. Ground-state solutions of these equations are by construction v-representable and effectively visualize bonding patterns in molecular systems.We show how these smooth density fragments can be used to correct errors of approximate density functionals like self-interaction or missing van der Waals interactions. To this end we introduce the many-pair expansion (MPE), which is a systematically improvable correction scheme converging to the exact energy. Possible applications in density embedding approaches and orbital-free DFT are also discussed.

AB - The recently introduced Self-Attractive Hartree (SAH) decomposition is a method to partition electron density into smooth localized fragments. The fragment densities are obtained through a regularized maximization of self-repulsion. The resulting set of eigenvalue equations resembles Kohn-Sham equations for electrons experiencing self-attractive Hartree potential and external potential common for all fragments. Ground-state solutions of these equations are by construction v-representable and effectively visualize bonding patterns in molecular systems.We show how these smooth density fragments can be used to correct errors of approximate density functionals like self-interaction or missing van der Waals interactions. To this end we introduce the many-pair expansion (MPE), which is a systematically improvable correction scheme converging to the exact energy. Possible applications in density embedding approaches and orbital-free DFT are also discussed.

M3 - Conference abstract in journal

VL - 256

JO - American Chemical Society. Abstracts of Papers (at the National Meeting)

JF - American Chemical Society. Abstracts of Papers (at the National Meeting)

SN - 0065-7727

ER -