Local and linear chemical reactivity response functions at finite temperature in density functional theory

Journal Article · Mon Dec 28 04:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4938422· OSTI ID:22493397

Franco-Pérez, Marco ^[1]; Vela, Alberto ^[2]

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1. Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario L8S 4M1 (Canada)
2. Departamento de Química, Centro de Investigación y de Estudios Avanzados (Cinvestav), Av. Instituto Politécnico Nacional 2508, México, D.F. 07360 (Mexico)

We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model.

• OSTI ID: 22493397
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 143; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CHEMICAL REACTIONS
DENSITY
DENSITY FUNCTIONAL METHOD
ELECTRON DENSITY
ELECTRONS
KERNELS
POTENTIALS
REACTIVITY
RESPONSE FUNCTIONS