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The HSAB principle from a finite-temperature grand-canonical perspective

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Abstract

We provide a new proof for Pearson’s hard/soft acid/base (HSAB) principle. Unlike alternative proofs, we do not presuppose a simplified parabolic dependence on the energy of the system with respect to changes in its number of electrons. Instead, we use the more physically grounded finite-temperature formulation of the grand-canonical ensemble. We show that under the usual assumptions regarding the chemical potentials and hardnesses of the involved species, the HSAB rule holds for a wide range of temperatures.

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Acknowledgements

RAMQ, TDK, and PWA thank NSERC, the Canada Research Chairs, and Compute Canada for support. RAMQ acknowledges support from Foreign Affairs, Trade and Development Canada in the form of an ELAP scholarship. CC acknowledges support by FONDECYT (Grant 1140313), Financiamiento Basal para Centros Científicos y Tecnológicos de Excelencia-FB0807, and Project RC-130006 CILIS, Granted by the Fondo de Innovación para la Competitividad del Ministerio de Economía, Fomento y Turismo de Chile. Discussions with Laritza Domínguez and Cristina González are gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON, Canada

    Ramón Alain Miranda-Quintana, Taewon David Kim & Paul W. Ayers

  2. Departamento de Física, Facultad de Ciencias, Universidad de Chile, Casilla 653, Santiago, Chile

    Carlos Cárdenas

  3. Centro para el desarrollo de la Nanociencias y Nanotecnología, CEDENNA, Av. Ecuador, 3493, Santiago, Chile

    Carlos Cárdenas

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  1. Ramón Alain Miranda-Quintana
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  2. Taewon David Kim
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  4. Paul W. Ayers
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Correspondence to Ramón Alain Miranda-Quintana.

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Miranda-Quintana, R.A., Kim, T.D., Cárdenas, C. et al. The HSAB principle from a finite-temperature grand-canonical perspective. Theor Chem Acc 136, 135 (2017). https://doi.org/10.1007/s00214-017-2167-y

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