Chan, Garnet Kin-Lic and Handy, Nicholas C. (1998) A new chemical concept: Shape chemical potentials. Journal of Chemical Physics, 109 (15). pp. 6287-6295. ISSN 0021-9606. doi:10.1063/1.477270. https://resolver.caltech.edu/CaltechAUTHORS:20160708-143819437
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Abstract
Within the density functional formalism, we introduce the shape chemical potential μ_i(^n) for subsystems, which in the limiting case of point subsystems, is a local chemical potential μ^n(r). It describes the electron withdrawing/donating ability of specified density fragments. The shape chemical potential does not equalize between subsystems, and provides a powerful new method to identify and describe local features of molecular systems. We explore the formal properties of μ_i(^n) especially with respect to discontinuities, and reconcile our results with Sanderson’s principle. We also perform preliminary calculations on model systems of atoms in molecules, and atomic shell structure, demonstrating how μ_i(^n) and μ^n(r), identify and characterize chemical features as regions of different shape chemical potential. We present arguments that shell structure, and other chemical features, are not ever obtainable within Thomas–Fermi-type theories.
Item Type: | Article | |||||||||
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Additional Information: | © 1998 American Institute of Physics. Received 16 April 1998; accepted 19 June 1998. G. K.-L. Chan acknowledges Professor J-P. Hansen and R. Daniel for interesting discussions. | |||||||||
Issue or Number: | 15 | |||||||||
DOI: | 10.1063/1.477270 | |||||||||
Record Number: | CaltechAUTHORS:20160708-143819437 | |||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20160708-143819437 | |||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
ID Code: | 68934 | |||||||||
Collection: | CaltechAUTHORS | |||||||||
Deposited By: | Donna Wrublewski | |||||||||
Deposited On: | 09 Jul 2016 04:56 | |||||||||
Last Modified: | 11 Nov 2021 04:06 |
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