Complexity Reduction in Large Quantum Systems: Fragment Identification and Population Analysis via a Local Optimized Minimal Basis

2016/12/31 by Stephan Mohr, Michel Masella, Laura E. Ratcliff +1
Computer Science · Mathematics · Medicine · Physics and Astronomy · #Advanced Chemical Physics Studies #Algorithm #Basis (linear algebra) #Biology #Computer science #Fragment (logic) #Identification (biology) #Mathematics #Medicine #Physics #Population #Quantum #Quantum Information and Cryptography #Quantum mechanics #Reduction (mathematics) #Spectroscopy and Quantum Chemical Studies #physics.chem-ph

paper · pdf · doi:10.1021/acs.jctc.7b00291

arxiv created 2017/07/10 · openalex publication_date 2017/07/21 · arxiv updated 2017/09/28 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

We present, within Kohn-Sham density functional theory calculations, a quantitative method to identify and assess the partitioning of a large quantum-mechanical system into fragments. We then show how within this framework simple generalizations of other well-known population analyses can be used to extract, from first-principles, reliable electrostatic multipoles for the identified fragments. Our approach reduces arbitrariness in the fragmentation procedure and enables the possibility to assess quantitatively whether the corresponding fragment multipoles can be interpreted as observable quantities associated with a system moiety. By applying our formalism within the code BigDFT, we show that the use of a minimal set of in situ-optimized basis functions allows at the same time a proper fragment definition and an accurate description of the electronic structure.

Citations

• Generalized Gradient Approximation Made Simple
• Calculations for millions of atoms with density functional theory: linear scaling shows its potential
• Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
• VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
• On the Non-Orthogonality Problem Connected with the Use of Atomic Wave Functions in the Theory of Molecules and Crystals
• Voronoi deformation density (VDD) charges: Assessment of the Mulliken, Bader, Hirshfeld, Weinhold, and VDD methods for charge analysis
• Efficient index handling of multidimensional periodic boundary conditions
• Self-Consistent Equations Including Exchange and Correlation Effects
• Complexity Reduction in Large Quantum Systems: Reliable Electrostatic Embedding for Multiscale Approaches via Optimized Minimal Basis Functions