Abstract
Grid-based energy density analysis (grid-EDA) that decomposes the total energy into atomic energies by a space-partitioning function is proposed. The kinetic energy, nuclear attraction, and exchange-correlation functional are evaluated on grid points and are split into atomic contributions. To reduce numerical errors in the conventional scheme of numerical integration, the electronic Coulomb and HF exchange interactions are evaluated by the pseudospectral method, which was first applied to an ab initio method by Friesner [Chem. Phys. Lett. 116, 39 (1985)], and are decomposed into atomic contributions. Grid-EDA using the pseudospectral method succeeds in ensuring less than 1 kcalmol error in total energies for small molecules and providing reliable atomic energy contributions for the problematic lithium cluster, which exhibits a strong basis-set dependence for Mulliken-type EDA. Also, site-dependent atomization energies are estimated by grid-EDA for cluster models such as Li48, C41 H60, and Mg32 O32. Grid-EDA reveals that these models imitate crystal environments reasonably because atomization energies estimated from the inner atoms of the models are close to the experimental cohesive energies.
| Original language | English |
|---|---|
| Article number | 034103 |
| Journal | Journal of Chemical Physics |
| Volume | 126 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - 2007 |
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ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
Cite this
Grid-based energy density analysis : Implementation and assessment. / Imamura, Yutaka; Takahashi, Asuka; Nakai, Hiromi.
In: Journal of Chemical Physics, Vol. 126, No. 3, 034103, 2007.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Grid-based energy density analysis
T2 - Implementation and assessment
AU - Imamura, Yutaka
AU - Takahashi, Asuka
AU - Nakai, Hiromi
PY - 2007
Y1 - 2007
N2 - Grid-based energy density analysis (grid-EDA) that decomposes the total energy into atomic energies by a space-partitioning function is proposed. The kinetic energy, nuclear attraction, and exchange-correlation functional are evaluated on grid points and are split into atomic contributions. To reduce numerical errors in the conventional scheme of numerical integration, the electronic Coulomb and HF exchange interactions are evaluated by the pseudospectral method, which was first applied to an ab initio method by Friesner [Chem. Phys. Lett. 116, 39 (1985)], and are decomposed into atomic contributions. Grid-EDA using the pseudospectral method succeeds in ensuring less than 1 kcalmol error in total energies for small molecules and providing reliable atomic energy contributions for the problematic lithium cluster, which exhibits a strong basis-set dependence for Mulliken-type EDA. Also, site-dependent atomization energies are estimated by grid-EDA for cluster models such as Li48, C41 H60, and Mg32 O32. Grid-EDA reveals that these models imitate crystal environments reasonably because atomization energies estimated from the inner atoms of the models are close to the experimental cohesive energies.
AB - Grid-based energy density analysis (grid-EDA) that decomposes the total energy into atomic energies by a space-partitioning function is proposed. The kinetic energy, nuclear attraction, and exchange-correlation functional are evaluated on grid points and are split into atomic contributions. To reduce numerical errors in the conventional scheme of numerical integration, the electronic Coulomb and HF exchange interactions are evaluated by the pseudospectral method, which was first applied to an ab initio method by Friesner [Chem. Phys. Lett. 116, 39 (1985)], and are decomposed into atomic contributions. Grid-EDA using the pseudospectral method succeeds in ensuring less than 1 kcalmol error in total energies for small molecules and providing reliable atomic energy contributions for the problematic lithium cluster, which exhibits a strong basis-set dependence for Mulliken-type EDA. Also, site-dependent atomization energies are estimated by grid-EDA for cluster models such as Li48, C41 H60, and Mg32 O32. Grid-EDA reveals that these models imitate crystal environments reasonably because atomization energies estimated from the inner atoms of the models are close to the experimental cohesive energies.
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U2 - 10.1063/1.2428290
DO - 10.1063/1.2428290
M3 - Article
VL - 126
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 3
M1 - 034103
ER -