TY - JOUR
T1 - One-body energy decomposition schemes revisited
T2 - Assessment of mulliken-, grid-, and conventional energy density analyses
AU - Kikuchi, Yasuaki
AU - Imamura, Yutaka
AU - Nakai, Hiromi
PY - 2009/7/9
Y1 - 2009/7/9
N2 - We propose a new energy density analysis (EDA) that evaluates atomic contributions of all energy terms, i.e., the kinetic, nuclear-attraction, Coulomb, and Hartree-Fock (HF) exchange and density functional theory (DFT) exchange-correlation energies using the Mulliken-type partitioning. Although widely used DFT exchangecorrelation functionals are nonlinear expressions in terms of density, they are decomposed into atomic contributions by focusing the linear part of the density. Numerical assessment on Mulliken-EDA, Grid-EDA, and conventional EDA has been carried out for the G2-1 set. Correlations between HF and DFT exchanges demonstrate that a consistent partitioning of all energy terms is essential for EDA. These numerical results confirm that the present Mulliken-EDA offers a more reasonable picture for the atomization process.
AB - We propose a new energy density analysis (EDA) that evaluates atomic contributions of all energy terms, i.e., the kinetic, nuclear-attraction, Coulomb, and Hartree-Fock (HF) exchange and density functional theory (DFT) exchange-correlation energies using the Mulliken-type partitioning. Although widely used DFT exchangecorrelation functionals are nonlinear expressions in terms of density, they are decomposed into atomic contributions by focusing the linear part of the density. Numerical assessment on Mulliken-EDA, Grid-EDA, and conventional EDA has been carried out for the G2-1 set. Correlations between HF and DFT exchanges demonstrate that a consistent partitioning of all energy terms is essential for EDA. These numerical results confirm that the present Mulliken-EDA offers a more reasonable picture for the atomization process.
KW - Becke's partitioning function
KW - Density functional theory
KW - Energy density analysis
KW - Grid-EDA
KW - Mulliken population analysis
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U2 - 10.1002/qua.22017
DO - 10.1002/qua.22017
M3 - Article
AN - SCOPUS:67649792233
VL - 109
SP - 2464
EP - 2473
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
SN - 0020-7608
IS - 11
ER -