Document Details
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Document Type |
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Article In Journal |
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Document Title |
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Analytical evaluation of Fukui functions and real-space linear response function Analytical evaluation of Fukui functions and real-space linear response function |
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Subject |
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physics |
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Document Language |
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English |
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Abstract |
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Many useful concepts developed within density functional theory provide much insight for the
understanding and prediction of chemical reactivity, one of the main aims in the field of conceptual
density functional theory. While approximate evaluations of such concepts exist, the analytical and
efficient evaluation is, however, challenging, because such concepts are usually expressed in terms of
functional derivatives with respect to the electron density, or partial derivatives with respect to the
number of electrons, complicating the connection to the computational variables of the Kohn-Sham
one-electron orbitals. Only recently, the analytical expressions for the chemical potential, one of the key
concepts, have been derived by Cohen, Mori-Sanchez, and Yang, based on the potential functional
theory formalism. In the present work, we obtain the analytical expressions for the real-space linear
response function using the coupled perturbed Kohn-Sham and generalized Kohn-Sham equations,
and the Fukui functions using the previous analytical expressions for chemical potentials of Cohen,
Mori-Sanchez, and Yang. The analytical expressions are exact within the given exchange-correlation
functional. They are applicable to all commonly used approximate functionals, such as local density
approximation (LDA), generalized gradient approximation (GGA), and hybrid functionals. The analytical
expressions obtained here for Fukui function and linear response functions, along with that for the
chemical potential by Cohen, Mori-Sanchez, and Yang, provide the rigorous and efficient evaluation of
the key quantities in conceptual density functional theory within the computational framework of the
Kohn-Sham and generalized Kohn-Sham approaches. Furthermore, the obtained analytical
expressions for Fukui functions, in conjunction with the linearity condition of the ground state energy as
a function of the fractional charges, also lead to new local conditions on the exact functionals,
expressed in terms of the second-order functional derivatives. We implemented the expressions and
demonstrate the efficacy with some atomic and molecular calculations, highlighting the importance of
relaxation effects |
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ISSN |
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0021-9606 |
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Journal Name |
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JOURNAL OF CHEMICAL PHYSICS |
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Volume |
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136 |
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Issue Number |
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14 |
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Publishing Year |
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1433 AH
2012 AD |
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Article Type |
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Article |
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Added Date |
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Tuesday, July 25, 2017 |
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Researchers
| Weitao Yang | Yang, Weitao | Investigator | Doctorate | |
| Aron J Cohen | Cohen, Aron J | Researcher | Doctorate | |
| Frank De Proft | De Proft, Frank | Researcher | Doctorate | |
| Paul Geerlings | Geerlings, Paul | Researcher | Doctorate | |
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