物理化学学报 >> 2018, Vol. 34 >> Issue (5): 514-518.doi: 10.3866/PKU.WHXB201710101

所属专题: 密度泛函理论中的化学概念特刊

论文 上一篇    下一篇

Generalized Hirshfeld Partitioning with Oriented and Promoted Proatoms

HEIDAR-ZADEH Farnaz1,2,3,AYERS Paul W.1,*()   

  1. 1 Department of Chemistry & Chemical Biology; McMaster University; Hamilton, Ontario, L8P 4Z2, Canada
    2 Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281 (S3), 9000 Gent, Belgium
    3 Center for Molecular Modeling, Ghent University, Technologiepark 903, 9052 Zwijnaarde, Belgium
  • 收稿日期:2017-08-31 发布日期:2018-01-24
  • 通讯作者: AYERS Paul W. E-mail:ayers@mcmaster.ca

Generalized Hirshfeld Partitioning with Oriented and Promoted Proatoms

Farnaz HEIDAR-ZADEH1,2,3,Paul W. AYERS1,*()   

  1. 1 Department of Chemistry & Chemical Biology; McMaster University; Hamilton, Ontario, L8P 4Z2, Canada
    2 Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281 (S3), 9000 Gent, Belgium
    3 Center for Molecular Modeling, Ghent University, Technologiepark 903, 9052 Zwijnaarde, Belgium
  • Received:2017-08-31 Published:2018-01-24
  • Contact: Paul W. AYERS E-mail:ayers@mcmaster.ca

摘要:

In this study, we show how to generalize Hirshfeld partitioning methods to possibly include non-spherical proatom densities. While this generalization is numerically challenging (requiring global optimization of a large number of parameters), it is conceptually appealing because it allows the proatoms to be pre-polarized, or even promoted, to a state that more closely resembles the atom in a molecule. This method is based on first characterizing the convex set of proatom densities associated with the degenerate ground states of isolated atoms and atomic ions. The preferred orientation of the proatoms' densities are then obtained by minimizing the information–theoretic distance between the promolecular and molecular densities. If contributions from excited states (and not just degenerate ground states) are included in the convex set, this method can describe promoted atoms. While the procedure is intractable in general, if one includes only atomic states that have differing electron-numbers and/or spins, the variational principle becomes a simple convex optimization with a single unique solution.

关键词: Hirshfeld partitioning, Stockholder atoms in molecules, Nonspherical proatoms, Information theory, Degenerate ground states, Promoted atomic reference states, Electron density, Conceptual density functional theory

Abstract:

In this study, we show how to generalize Hirshfeld partitioning methods to possibly include non-spherical proatom densities. While this generalization is numerically challenging (requiring global optimization of a large number of parameters), it is conceptually appealing because it allows the proatoms to be pre-polarized, or even promoted, to a state that more closely resembles the atom in a molecule. This method is based on first characterizing the convex set of proatom densities associated with the degenerate ground states of isolated atoms and atomic ions. The preferred orientation of the proatoms' densities are then obtained by minimizing the information–theoretic distance between the promolecular and molecular densities. If contributions from excited states (and not just degenerate ground states) are included in the convex set, this method can describe promoted atoms. While the procedure is intractable in general, if one includes only atomic states that have differing electron-numbers and/or spins, the variational principle becomes a simple convex optimization with a single unique solution.

Key words: Hirshfeld partitioning, Stockholder atoms in molecules, Nonspherical proatoms, Information theory, Degenerate ground states, Promoted atomic reference states, Electron density, Conceptual density functional theory