Incorporation of charge transfer into the explicit polarization fragment method by grand canonical density functional theory

Miho Isegawa, Jiali Gao, Donald G. Truhlar

研究成果: ジャーナルへの寄稿記事

13 引用 (Scopus)

抄録

Molecular fragmentation algorithms provide a powerful approach to extending electronic structure methods to very large systems. Here we present a method for including charge transfer between molecular fragments in the explicit polarization (X-Pol) fragment method for calculating potential energy surfaces. In the conventional X-Pol method, the total charge of each fragment is preserved, and charge transfer between fragments is not allowed. The description of charge transfer is made possible by treating each fragment as an open system with respect to the number of electrons. To achieve this, we applied Mermins finite temperature method to the X-Pol wave function. In the application of this method to X-Pol, the fragments are open systems that partially equilibrate their number of electrons through a quasithermodynamics electron reservoir. The number of electrons in a given fragment can take a fractional value, and the electrons of each fragment obey the Fermi-Dirac distribution. The equilibrium state for the electrons is determined by electronegativity equalization with conservation of the total number of electrons. The amount of charge transfer is controlled by re-interpreting the temperature parameter in the Fermi-Dirac distribution function as a coupling strength parameter. We determined this coupling parameter so as to reproduce the charge transfer energy obtained by block localized energy decomposition analysis. We apply the new method to ten systems, and we show that it can yield reasonable approximations to potential energy profiles, to charge transfer stabilization energies, and to the direction and amount of charge transferred.

元の言語英語
記事番号084107
ジャーナルJournal of Chemical Physics
135
発行部数8
DOI
出版物ステータス出版済み - 8 28 2011
外部発表Yes

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Density functional theory
Charge transfer
charge transfer
fragments
Polarization
density functional theory
Electrons
polarization
electrons
Open systems
potential energy
Electronegativity
Potential energy surfaces
Wave functions
Potential energy
Electronic structure
Distribution functions
Conservation
Stabilization
energy

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

これを引用

Incorporation of charge transfer into the explicit polarization fragment method by grand canonical density functional theory. / Isegawa, Miho; Gao, Jiali; Truhlar, Donald G.

:: Journal of Chemical Physics, 巻 135, 番号 8, 084107, 28.08.2011.

研究成果: ジャーナルへの寄稿記事

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