Density matrix embedding: A strong-coupling quantum embedding theory

Gerald Knizia, Garnet Kin Lic Chan

Research output: Contribution to journalArticle

118 Citations (Scopus)

Abstract

We extend our density matrix embedding theory (DMET) [Phys. Rev. Lett.2012, 109, 186404] from lattice models to the full chemical Hamiltonian. DMET allows the many-body embedding of arbitrary fragments of a quantum system, even when such fragments are open systems and strongly coupled to their environment (e.g., by covalent bonds). In DMET, empirical approaches to strong coupling, such as link atoms or boundary regions, are replaced by a small, rigorous quantum bath designed to reproduce the entanglement between a fragment and its environment. We describe the theory and demonstrate its feasibility in strongly correlated hydrogen ring and grid models; these are not only beyond the scope of traditional embeddings but even challenge conventional quantum chemistry methods themselves. We find that DMET correctly describes the notoriously difficult symmetric dissociation of a 4 × 3 hydrogen atom grid, even when the treated fragments are as small as single hydrogen atoms. We expect that DMET will open up new ways of treating complex strongly coupled, strongly correlated systems in terms of their individual fragments.

Original languageEnglish (US)
Pages (from-to)1428-1432
Number of pages5
JournalJournal of Chemical Theory and Computation
Volume9
Issue number3
DOIs
StatePublished - Mar 12 2013

Fingerprint

Quantum theory
embedding
fragments
Hydrogen
Atoms
Hamiltonians
Quantum chemistry
hydrogen atoms
Covalent bonds
Open systems
grids
covalent bonds
quantum chemistry
baths
dissociation
rings
hydrogen
atoms

All Science Journal Classification (ASJC) codes

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

@article{aa4fd988450f4ac99dba15e9bae70858,
title = "Density matrix embedding: A strong-coupling quantum embedding theory",
abstract = "We extend our density matrix embedding theory (DMET) [Phys. Rev. Lett.2012, 109, 186404] from lattice models to the full chemical Hamiltonian. DMET allows the many-body embedding of arbitrary fragments of a quantum system, even when such fragments are open systems and strongly coupled to their environment (e.g., by covalent bonds). In DMET, empirical approaches to strong coupling, such as link atoms or boundary regions, are replaced by a small, rigorous quantum bath designed to reproduce the entanglement between a fragment and its environment. We describe the theory and demonstrate its feasibility in strongly correlated hydrogen ring and grid models; these are not only beyond the scope of traditional embeddings but even challenge conventional quantum chemistry methods themselves. We find that DMET correctly describes the notoriously difficult symmetric dissociation of a 4 × 3 hydrogen atom grid, even when the treated fragments are as small as single hydrogen atoms. We expect that DMET will open up new ways of treating complex strongly coupled, strongly correlated systems in terms of their individual fragments.",
author = "Gerald Knizia and Chan, {Garnet Kin Lic}",
year = "2013",
month = "3",
day = "12",
doi = "10.1021/ct301044e",
language = "English (US)",
volume = "9",
pages = "1428--1432",
journal = "Journal of Chemical Theory and Computation",
issn = "1549-9618",
publisher = "American Chemical Society",
number = "3",

}

Density matrix embedding : A strong-coupling quantum embedding theory. / Knizia, Gerald; Chan, Garnet Kin Lic.

In: Journal of Chemical Theory and Computation, Vol. 9, No. 3, 12.03.2013, p. 1428-1432.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Density matrix embedding

T2 - A strong-coupling quantum embedding theory

AU - Knizia, Gerald

AU - Chan, Garnet Kin Lic

PY - 2013/3/12

Y1 - 2013/3/12

N2 - We extend our density matrix embedding theory (DMET) [Phys. Rev. Lett.2012, 109, 186404] from lattice models to the full chemical Hamiltonian. DMET allows the many-body embedding of arbitrary fragments of a quantum system, even when such fragments are open systems and strongly coupled to their environment (e.g., by covalent bonds). In DMET, empirical approaches to strong coupling, such as link atoms or boundary regions, are replaced by a small, rigorous quantum bath designed to reproduce the entanglement between a fragment and its environment. We describe the theory and demonstrate its feasibility in strongly correlated hydrogen ring and grid models; these are not only beyond the scope of traditional embeddings but even challenge conventional quantum chemistry methods themselves. We find that DMET correctly describes the notoriously difficult symmetric dissociation of a 4 × 3 hydrogen atom grid, even when the treated fragments are as small as single hydrogen atoms. We expect that DMET will open up new ways of treating complex strongly coupled, strongly correlated systems in terms of their individual fragments.

AB - We extend our density matrix embedding theory (DMET) [Phys. Rev. Lett.2012, 109, 186404] from lattice models to the full chemical Hamiltonian. DMET allows the many-body embedding of arbitrary fragments of a quantum system, even when such fragments are open systems and strongly coupled to their environment (e.g., by covalent bonds). In DMET, empirical approaches to strong coupling, such as link atoms or boundary regions, are replaced by a small, rigorous quantum bath designed to reproduce the entanglement between a fragment and its environment. We describe the theory and demonstrate its feasibility in strongly correlated hydrogen ring and grid models; these are not only beyond the scope of traditional embeddings but even challenge conventional quantum chemistry methods themselves. We find that DMET correctly describes the notoriously difficult symmetric dissociation of a 4 × 3 hydrogen atom grid, even when the treated fragments are as small as single hydrogen atoms. We expect that DMET will open up new ways of treating complex strongly coupled, strongly correlated systems in terms of their individual fragments.

UR - http://www.scopus.com/inward/record.url?scp=84874906488&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84874906488&partnerID=8YFLogxK

U2 - 10.1021/ct301044e

DO - 10.1021/ct301044e

M3 - Article

AN - SCOPUS:84874906488

VL - 9

SP - 1428

EP - 1432

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

SN - 1549-9618

IS - 3

ER -