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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Bibliographic Details
Published in:The Journal of chemical physics 2014-06, Vol.140 (24), p.244105-244105
Main Authors: Ohwaki, Tsukuru, Otani, Minoru, Ozaki, Taisuke
Format: Article
Language:English
Subjects:
CARBONIC ACID ESTERS
CHEMICAL BONDS
CHEMICAL REACTIONS
Computer simulation
DENSITY FUNCTIONAL METHOD
Density functional theory
DENSITY MATRIX
ELECTROLYTES
ELECTRONIC STRUCTURE
First principles
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
LIQUIDS
Molecular dynamics
MOLECULAR DYNAMICS METHOD
Orbitals
Organic chemistry
Propylene
Quantitative analysis
SIMULATION
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Summary: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