A method of orbital analysis for large-scale first-principles simulations

An efficient method of calculating the natural bond orbitals (NBOs) based on a truncation of the entire density matrix of a whole system is presented for large-scale density functional theory calculations. The method recovers an orbital picture for O(N) electronic structure methods which directly ev...

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Veröffentlicht in:The Journal of chemical physics 2014-06, Vol.140 (24), p.244105-244105
Hauptverfasser: Ohwaki, Tsukuru, Otani, Minoru, Ozaki, Taisuke
Format: Artikel
Sprache:eng
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Zusammenfassung:An efficient method of calculating the natural bond orbitals (NBOs) based on a truncation of the entire density matrix of a whole system is presented for large-scale density functional theory calculations. The method recovers an orbital picture for O(N) electronic structure methods which directly evaluate the density matrix without using Kohn-Sham orbitals, thus enabling quantitative analysis of chemical reactions in large-scale systems in the language of localized Lewis-type chemical bonds. With the density matrix calculated by either an exact diagonalization or O(N) method, the computational cost is O(1) for the calculation of NBOs associated with a local region where a chemical reaction takes place. As an illustration of the method, we demonstrate how an electronic structure in a local region of interest can be analyzed by NBOs in a large-scale first-principles molecular dynamics simulation for a liquid electrolyte bulk model (propylene carbonate + LiBF4).
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4884119