TY - JOUR
T1 - Comparison of Density-Matrix Corrections to Density Functional Theory
AU - Gibney, Daniel
AU - Boyn, Jan Niklas
AU - Mazziotti, David A.
N1 - Publisher Copyright:
© 2022 American Chemical Society.
PY - 2022/11/8
Y1 - 2022/11/8
N2 - Density functional theory (DFT), one of the most widely utilized methods available to computational chemistry, fails to describe systems with statically correlated electrons. To address this shortcoming, in previous work, we transformed DFT into a one-electron reduced density matrix theory (1-RDMFT) via the inclusion of a quadratic one-electron reduced density matrix (1-RDM) correction. Here, we combine our 1-RDMFT approach with different DFT functionals as well as Hartree-Fock to elucidate the method's dependence on the underlying functional selection. Furthermore, we generalize the information density matrix functional theory (iDMFT), recently developed as a correction to the Hartree-Fock method, by incorporating density functionals in place of the Hartree-Fock functional. We relate iDMFT mathematically to our approach and benchmark the two with a common set of functionals and systems.
AB - Density functional theory (DFT), one of the most widely utilized methods available to computational chemistry, fails to describe systems with statically correlated electrons. To address this shortcoming, in previous work, we transformed DFT into a one-electron reduced density matrix theory (1-RDMFT) via the inclusion of a quadratic one-electron reduced density matrix (1-RDM) correction. Here, we combine our 1-RDMFT approach with different DFT functionals as well as Hartree-Fock to elucidate the method's dependence on the underlying functional selection. Furthermore, we generalize the information density matrix functional theory (iDMFT), recently developed as a correction to the Hartree-Fock method, by incorporating density functionals in place of the Hartree-Fock functional. We relate iDMFT mathematically to our approach and benchmark the two with a common set of functionals and systems.
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U2 - 10.1021/acs.jctc.2c00625
DO - 10.1021/acs.jctc.2c00625
M3 - Article
C2 - 36287002
AN - SCOPUS:85140984132
SN - 1549-9618
VL - 18
SP - 6600
EP - 6607
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 11
ER -