物理化学学报 >> 2018, Vol. 34 >> Issue (5): 492-496.doi: 10.3866/PKU.WHXB201709221

所属专题: 密度泛函理论中的化学概念特刊

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Phase Space View of Ensembles of Excited States

NAGY Ágnes*()   

  • 收稿日期:2017-08-11 发布日期:2018-01-24
  • 通讯作者: NAGY ágnes E-mail:anagy@phys.unideb.hu
  • 基金资助:
    The project was supported by the National Research, Development and Innovation Fund of Hungary, Financed under the 123988 Funding Scheme(51335008)

Phase Space View of Ensembles of Excited States

Ágnes NAGY*()   

  • Received:2017-08-11 Published:2018-01-24
  • Contact: ágnes NAGY E-mail:anagy@phys.unideb.hu
  • Supported by:
    The project was supported by the National Research, Development and Innovation Fund of Hungary, Financed under the 123988 Funding Scheme(51335008)

摘要:

The density functional theory and its extension to ensembles of excited states can be formalized as thermodynamics. However, these theories are not unique because one of their key quantities, the kinetic energy density, can be defined in several ways. Usually, the everywhere positive gradient form is applied; however, other forms are also acceptable, provided they integrate to the true kinetic energy. Recently, a kinetic energy density of the ground-state theory maximizing the information entropy has been proposed. Here, ensemble kinetic energy density, leading to extremum information entropy, is derived via constrained search. The corresponding ensemble temperature is found to be constant.

关键词: Ensemble of excited states, Kinetic energy density, Constrained search, Ensemble temperature

Abstract:

The density functional theory and its extension to ensembles of excited states can be formalized as thermodynamics. However, these theories are not unique because one of their key quantities, the kinetic energy density, can be defined in several ways. Usually, the everywhere positive gradient form is applied; however, other forms are also acceptable, provided they integrate to the true kinetic energy. Recently, a kinetic energy density of the ground-state theory maximizing the information entropy has been proposed. Here, ensemble kinetic energy density, leading to extremum information entropy, is derived via constrained search. The corresponding ensemble temperature is found to be constant.

Key words: Ensemble of excited states, Kinetic energy density, Constrained search, Ensemble temperature