A unified density matrix functional construction of quantum baths in density matrix embedding theory beyond the mean-field approximation - Archive ouverte HAL
Article Dans Une Revue The Journal of Chemical Physics Année : 2023

A unified density matrix functional construction of quantum baths in density matrix embedding theory beyond the mean-field approximation

Sajanthan Sekaran
Oussama Bindech
Emmanuel Fromager

Résumé

The equivalence in one-electron quantum baths between the practical implementation of density matrix embedding theory (DMET) and the more recent Householder-transformed density matrix functional embedding theory has been shown previously in the standard but special case where the reference full-size (one-electron reduced) density matrix, from which the bath is constructed, is idempotent [S. Yalouz et al., J. Chem. Phys. 157, 214112 (2022)]. We prove mathematically that the equivalence remains valid when the density matrix is not idempotent anymore, thus allowing for the construction of correlated (one-electron) quantum baths. A density-matrix functional exactification of DMET is derived within the present unified quantum embedding formalism. Numerical examples reveal that the embedding cluster can be quite sensitive to the level of density-matrix functional approximation used for computing the reference density matrix.

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Chimie

Dates et versions

hal-04170578 , version 1 (25-07-2023)

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Sajanthan Sekaran, Oussama Bindech, Emmanuel Fromager. A unified density matrix functional construction of quantum baths in density matrix embedding theory beyond the mean-field approximation. The Journal of Chemical Physics, 2023, 159 (3), ⟨10.1063/5.0157746⟩. ⟨hal-04170578⟩
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