On the second-order functional structure of the chemical potential in conceptual density functional theory

The second-order functional structure of the chemical potential is examined within conceptual density functional theory by treating μ[N, v(r)] as a functional of the electron number and the external potential. In close analogy with the nonperturbative functional expansion of the total energy introduced by Liu and Parr, the chemical potential admits an explicit functional form up to second order that does not rely on a Taylor expansion about a reference state. This representation organizes established first- and second-order response descriptors into a unified response-theoretical framework, where the linear terms recover the standard hardness and Fukui function contributions, while quadratic terms encode nonlinear charge effects and nonlocal response through the hyperhardness, charge sensitivity, and response kernel. The resulting formulation clarifies the hierarchical organization of response properties associated with the chemical potential and provides a complementary perspective on electronegativity equalization within conceptual density functional theory.

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Publication Details

Journal
The Journal of Chemical Physics
Published
2026-03-09
DOI
https://doi.org/10.1063/5.0321646
Primary Topic
Advanced Chemical Physics Studies
Type
article
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article

On the second-order functional structure of the chemical potential in conceptual density functional theory

Eduardo E. Chamorro
The Journal of Chemical Physics
Advanced Chemical Physics Studies
article

On the second-order functional structure of the chemical potential in conceptual density functional theory

Eduardo E. Chamorro
article en

Abstract

The second-order functional structure of the chemical potential is examined within conceptual density functional theory by treating μ[N, v(r)] as a functional of the electron number and the external potential. In close analogy with the nonperturbative functional expansion of the total energy introduced by Liu and Parr, the chemical potential admits an explicit functional form up to second order that does not rely on a Taylor expansion about a reference state. This representation organizes established first- and second-order response descriptors into a unified response-theoretical framework, where the linear terms recover the standard hardness and Fukui function contributions, while quadratic terms encode nonlinear charge effects and nonlocal response through the hyperhardness, charge sensitivity, and response kernel. The resulting formulation clarifies the hierarchical organization of response properties associated with the chemical potential and provides a complementary perspective on electronegativity equalization within conceptual density functional theory.

The Journal of Chemical PhysicsVol. 164(10)
San Sebastián University (CL)
Openalex Percentile: Top 27%
Advanced Chemical Physics Studies
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On the second-order functional structure of the chemical potential in conceptual density functional theory — Eduardo E. Chamorro · The Journal of Chemical Physics (2026) | TGRS Research Map | TGRS