The Influence of the Exchange-Correlation Functional on the Non-Interacting Kinetic Energy and Its Implications for Orbital-Free Density Functional Approximations

Citation: FINZEL Kati., BULTINCK Patrick.. The Influence of the Exchange-Correlation Functional on the Non-Interacting Kinetic Energy and Its Implications for Orbital-Free Density Functional Approximations[J]. Acta Physico-Chimica Sinica, 2018, 34(6): 650-655. doi: 10.3866/PKU.WHXB201710251 shu

The Influence of the Exchange-Correlation Functional on the Non-Interacting Kinetic Energy and Its Implications for Orbital-Free Density Functional Approximations

FINZELKati. ^, ,
BULTINCKPatrick.

.
Department of Inorganic and Physical Chemistry, Ghent University, 281 Krijgslaan, 9000 Ghent, Belgium

通讯作者: FINZELKati., Kati.Finzel@UGent.be

摘要: In this work it is shown that the kinetic energy and the exchange-correlation energy are mutual dependent on each other. This aspect is first derived in an orbital-free context. It is shown that the total Fermi potential depends on the density only, the individual parts, the Pauli kinetic energy and the exchange-correlation energy, however, are orbital dependent and as such mutually influence each other. The numerical investigation is performed for the orbital-based non-interacting Kohn-Sham system in order to avoid additional effects due to further approximations of the kinetic energy. The numerical influence of the exchange-correlation functional on the non-interacting kinetic energy is shown to be of the order of a few Hartrees. For chemical purposes, however, the energetic performance as a function of the nuclear coordinates is much more important than total energies. Therefore, the effect on the bond dissociation curve was studied exemplarily for the carbon monoxide. The data reveals that, the mutual influence between the exchange-correlation functional and the kinetic energy has a significant influence on bond dissociation energies and bond distances. Therefore, the effect of the exchange-correlation treatment must be considered in the design of orbital-free density functional approximations for the kinetic energy.

关键词:

English

The Influence of the Exchange-Correlation Functional on the Non-Interacting Kinetic Energy and Its Implications for Orbital-Free Density Functional Approximations

FINZEL Kati. ^, ,
BULTINCK Patrick.

Department of Inorganic and Physical Chemistry, Ghent University, 281 Krijgslaan, 9000 Ghent, Belgium

Corresponding author: FINZEL Kati., Kati.Finzel@UGent.be

Received Date: 25 August 2017
Accepted Date: 19 October 2017
Revised Date: 27 September 2017
Available Online: 15 June 2018
Fund Project:
The project was supported by the Fund for Scientific Research in Flanders (FWO-Vlaanderen) for Research Grant G021115N

Abstract: In this work it is shown that the kinetic energy and the exchange-correlation energy are mutual dependent on each other. This aspect is first derived in an orbital-free context. It is shown that the total Fermi potential depends on the density only, the individual parts, the Pauli kinetic energy and the exchange-correlation energy, however, are orbital dependent and as such mutually influence each other. The numerical investigation is performed for the orbital-based non-interacting Kohn-Sham system in order to avoid additional effects due to further approximations of the kinetic energy. The numerical influence of the exchange-correlation functional on the non-interacting kinetic energy is shown to be of the order of a few Hartrees. For chemical purposes, however, the energetic performance as a function of the nuclear coordinates is much more important than total energies. Therefore, the effect on the bond dissociation curve was studied exemplarily for the carbon monoxide. The data reveals that, the mutual influence between the exchange-correlation functional and the kinetic energy has a significant influence on bond dissociation energies and bond distances. Therefore, the effect of the exchange-correlation treatment must be considered in the design of orbital-free density functional approximations for the kinetic energy.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

The Influence of the Exchange-Correlation Functional on the Non-Interacting Kinetic Energy and Its Implications for Orbital-Free Density Functional Approximations

通讯作者: FINZELKati., Kati.Finzel@UGent.be

English

The Influence of the Exchange-Correlation Functional on the Non-Interacting Kinetic Energy and Its Implications for Orbital-Free Density Functional Approximations

Corresponding author: FINZEL Kati., Kati.Finzel@UGent.be

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The Influence of the Exchange-Correlation Functional on the Non-Interacting Kinetic Energy and Its Implications for Orbital-Free Density Functional Approximations

通讯作者: FINZELKati., Kati.Finzel@UGent.be

English

The Influence of the Exchange-Correlation Functional on the Non-Interacting Kinetic Energy and Its Implications for Orbital-Free Density Functional Approximations

Corresponding author: FINZEL Kati., Kati.Finzel@UGent.be

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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