Molecular interactions from the density functional theory for chemical reactivity: Interaction chemical potential, hardness, and reactivity principles

Miranda-Quintana, Ramón Alain; Heidar-Zadeh, Farnaz; Fias, Stijn; Chapman, Allison A.; Liu, Shubin; Morell, Christophe; Gómez, Tatiana; Cárdenas, Carlos; Ayers, Paul W.

doi:10.3389/fchem.2022.929464

Title: Molecular interactions from the density functional theory for chemical reactivity: Interaction chemical potential, hardness, and reactivity principles

Journal Article · 21 July 2022 · Frontiers in Chemistry

DOI: https://doi.org/10.3389/fchem.2022.929464 · OSTI ID:1904560

Miranda-Quintana, Ramón Alain ^[1]; Heidar-Zadeh, Farnaz ^[2]; Fias, Stijn ^[3]; Chapman, Allison A. ^[3]; Liu, Shubin ^[4]; Morell, Christophe ^[5]; Gómez, Tatiana ^[6]; Cárdenas, Carlos ^[7]; Ayers, Paul W. ^[3]

University of Florida, Gainesville, FL (United States); Univ. of Florida, Gainesville, FL (United States)
Queen's University, Kingston, ON (Canada)
McMaster University, Hamilton, ON (Canada)
University of North Carolina, Charlotte, NC (United States)
Université Claude-Bernard Lyon 1 (UCBL) (France)
Universidad Autonoma de Chile, Santiago (Chile)
Universidad de Chile, Santiago (Chile); Centro para el desarrollo de la Nanociencias y Nanotecnologia, CEDENNA, Santiago (Chile)

In the first paper of this series, the authors derived an expression for the interaction energy between two reagents in terms of the chemical reactivity indicators that can be derived from density functional perturbation theory. While negative interaction energies can explain reactivity, reactivity is often more simply explained using the “|dμ| big is good” rule or the maximum hardness principle. Expressions for the change in chemical potential (μ) and hardness when two reagents interact are derived. A partial justification for the maximum hardness principle is that the terms that appear in the interaction energy expression often reappear in the expression for the interaction hardness, but with opposite sign.

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Research Organization:: University of Florida, Gainesville, FL (United States); University of North Carolina, Chapel Hill, NC (United States)

Sponsoring Organization:: Canada Research Chairs; Compute Canada; National Fund for Scientific and Technological Development (FONDECYT); Natural Sciences and Engineering Research Council of Canada (NSERC); USDOE Office of Science (SC), Basic Energy Sciences (BES); University of Florida

Grant/Contract Number:: SC0001011

OSTI ID:: 1904560

Journal Information:: Frontiers in Chemistry, Journal Name: Frontiers in Chemistry Vol. 10; ISSN 2296-2646

Publisher:: Frontiers Research FoundationCopyright Statement

Country of Publication:: United States

Language:: English

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Legendre-transform functionals for spin-density-functional theory Ayers, Paul W.; Yang, Weitao The Journal of Chemical Physics, Vol. 124, Issue 22 https://doi.org/10.1063/1.2200884	journal	June 2006
Woodward-Hoffmann rules in density functional theory: Initial hardness response De Proft, Frank; Ayers, Paul W.; Fias, Stijn The Journal of Chemical Physics, Vol. 125, Issue 21 https://doi.org/10.1063/1.2387953	journal	December 2006
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Critical thoughts on computing atom condensed Fukui functions Bultinck, Patrick; Fias, Stijn; Van Alsenoy, Christian The Journal of Chemical Physics, Vol. 127, Issue 3 https://doi.org/10.1063/1.2749518	journal	July 2007
Universal mathematical identities in density functional theory: Results from three different spin-resolved representations Pérez, P.; Chamorro, E.; Ayers, Paul W. The Journal of Chemical Physics, Vol. 128, Issue 20 https://doi.org/10.1063/1.2916714	journal	May 2008
Local hardness equalization: Exploiting the ambiguity Ayers, Paul W.; Parr, Robert G. The Journal of Chemical Physics, Vol. 128, Issue 18 https://doi.org/10.1063/1.2918731	journal	May 2008
Relationships between the third-order reactivity indicators in chemical density-functional theory Cárdenas, Carlos; Echegaray, Eleonora; Chakraborty, Debajit The Journal of Chemical Physics, Vol. 130, Issue 24 https://doi.org/10.1063/1.3151599	journal	June 2009
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Density-based energy decomposition analysis for intermolecular interactions with variationally determined intermediate state energies Wu, Qin; Ayers, Paul W.; Zhang, Yingkai The Journal of Chemical Physics, Vol. 131, Issue 16 https://doi.org/10.1063/1.3253797	journal	October 2009
Reactivity indicators for degenerate states in the density-functional theoretic chemical reactivity theory Cárdenas, Carlos; Ayers, Paul W.; Cedillo, Andrés The Journal of Chemical Physics, Vol. 134, Issue 17 https://doi.org/10.1063/1.3585610	journal	May 2011
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Revisiting the definition of the electronic chemical potential, chemical hardness, and softness at finite temperatures Franco-Pérez, Marco; Gázquez, José L.; Ayers, Paul W. The Journal of Chemical Physics, Vol. 143, Issue 15 https://doi.org/10.1063/1.4932539	journal	October 2015
Local and linear chemical reactivity response functions at finite temperature in density functional theory Franco-Pérez, Marco; Ayers, Paul W.; Gázquez, José L. The Journal of Chemical Physics, Vol. 143, Issue 24 https://doi.org/10.1063/1.4938422	journal	December 2015
Interpolation of property-values between electron numbers is inconsistent with ensemble averaging Miranda-Quintana, Ramón Alain; Ayers, Paul W. The Journal of Chemical Physics, Vol. 144, Issue 24 https://doi.org/10.1063/1.4953557	journal	June 2016
Communication: Two types of flat-planes conditions in density functional theory Yang, Xiaotian Derrick; Patel, Anand H. G.; Miranda-Quintana, Ramón Alain The Journal of Chemical Physics, Vol. 145, Issue 3 https://doi.org/10.1063/1.4958636	journal	July 2016
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Finite temperature grand canonical ensemble study of the minimum electrophilicity principle Miranda-Quintana, Ramón Alain; Chattaraj, Pratim K.; Ayers, Paul W. The Journal of Chemical Physics, Vol. 147, Issue 12 https://doi.org/10.1063/1.4996443	journal	September 2017
Thermodynamic responses of electronic systems Franco-Pérez, Marco; Ayers, Paul W.; Gázquez, José L. The Journal of Chemical Physics, Vol. 147, Issue 9 https://doi.org/10.1063/1.4999761	journal	September 2017
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Molecular Interactions From the Density Functional Theory for Chemical Reactivity: The Interaction Energy Between Two-Reagents Miranda-Quintana, Ramón Alain; Heidar-Zadeh, Farnaz; Fias, Stijn Frontiers in Chemistry, Vol. 10 https://doi.org/10.3389/fchem.2022.906674	journal	June 2022

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variational principle

Title: Molecular interactions from the density functional theory for chemical reactivity: Interaction chemical potential, hardness, and reactivity principles

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