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Consistent inclusion of continuum solvation in energy decomposition analysis: theory and application to molecular CO(2) reduction catalysts

To facilitate computational investigation of intermolecular interactions in the solution phase, we report the development of ALMO-EDA(solv), a scheme that allows the application of continuum solvent models within the framework of energy decomposition analysis (EDA) based on absolutely localized mole...

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Autores principales: Mao, Yuezhi, Loipersberger, Matthias, Kron, Kareesa J., Derrick, Jeffrey S., Chang, Christopher J., Sharada, Shaama Mallikarjun, Head-Gordon, Martin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179122/
https://www.ncbi.nlm.nih.gov/pubmed/34163903
http://dx.doi.org/10.1039/d0sc05327a
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author Mao, Yuezhi
Loipersberger, Matthias
Kron, Kareesa J.
Derrick, Jeffrey S.
Chang, Christopher J.
Sharada, Shaama Mallikarjun
Head-Gordon, Martin
author_facet Mao, Yuezhi
Loipersberger, Matthias
Kron, Kareesa J.
Derrick, Jeffrey S.
Chang, Christopher J.
Sharada, Shaama Mallikarjun
Head-Gordon, Martin
author_sort Mao, Yuezhi
collection PubMed
description To facilitate computational investigation of intermolecular interactions in the solution phase, we report the development of ALMO-EDA(solv), a scheme that allows the application of continuum solvent models within the framework of energy decomposition analysis (EDA) based on absolutely localized molecular orbitals (ALMOs). In this scheme, all the quantum mechanical states involved in the variational EDA procedure are computed with the presence of solvent environment so that solvation effects are incorporated in the evaluation of all its energy components. After validation on several model complexes, we employ ALMO-EDA(solv) to investigate substituent effects on two classes of complexes that are related to molecular CO(2) reduction catalysis. For [FeTPP(CO(2)-κC)](2−) (TPP = tetraphenylporphyrin), we reveal that two ortho substituents which yield most favorable CO(2) binding, –N(CH(3))(3)(+) (TMA) and –OH, stabilize the complex via through-structure and through-space mechanisms, respectively. The coulombic interaction between the positively charged TMA group and activated CO(2) is found to be largely attenuated by the polar solvent. Furthermore, we also provide computational support for the design strategy of utilizing bulky, flexible ligands to stabilize activated CO(2)via long-range Coulomb interactions, which creates biomimetic solvent-inaccessible “pockets” in that electrostatics is unscreened. For the reactant and product complexes associated with the electron transfer from the p-terphenyl radical anion to CO(2), we demonstrate that the double terminal substitution of p-terphenyl by electron-withdrawing groups considerably strengthens the binding in the product state while moderately weakens that in the reactant state, which are both dominated by the substituent tuning of the electrostatics component. These applications illustrate that this new extension of ALMO-EDA provides a valuable means to unravel the nature of intermolecular interactions and quantify their impacts on chemical reactivity in solution.
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spelling pubmed-81791222021-06-22 Consistent inclusion of continuum solvation in energy decomposition analysis: theory and application to molecular CO(2) reduction catalysts Mao, Yuezhi Loipersberger, Matthias Kron, Kareesa J. Derrick, Jeffrey S. Chang, Christopher J. Sharada, Shaama Mallikarjun Head-Gordon, Martin Chem Sci Chemistry To facilitate computational investigation of intermolecular interactions in the solution phase, we report the development of ALMO-EDA(solv), a scheme that allows the application of continuum solvent models within the framework of energy decomposition analysis (EDA) based on absolutely localized molecular orbitals (ALMOs). In this scheme, all the quantum mechanical states involved in the variational EDA procedure are computed with the presence of solvent environment so that solvation effects are incorporated in the evaluation of all its energy components. After validation on several model complexes, we employ ALMO-EDA(solv) to investigate substituent effects on two classes of complexes that are related to molecular CO(2) reduction catalysis. For [FeTPP(CO(2)-κC)](2−) (TPP = tetraphenylporphyrin), we reveal that two ortho substituents which yield most favorable CO(2) binding, –N(CH(3))(3)(+) (TMA) and –OH, stabilize the complex via through-structure and through-space mechanisms, respectively. The coulombic interaction between the positively charged TMA group and activated CO(2) is found to be largely attenuated by the polar solvent. Furthermore, we also provide computational support for the design strategy of utilizing bulky, flexible ligands to stabilize activated CO(2)via long-range Coulomb interactions, which creates biomimetic solvent-inaccessible “pockets” in that electrostatics is unscreened. For the reactant and product complexes associated with the electron transfer from the p-terphenyl radical anion to CO(2), we demonstrate that the double terminal substitution of p-terphenyl by electron-withdrawing groups considerably strengthens the binding in the product state while moderately weakens that in the reactant state, which are both dominated by the substituent tuning of the electrostatics component. These applications illustrate that this new extension of ALMO-EDA provides a valuable means to unravel the nature of intermolecular interactions and quantify their impacts on chemical reactivity in solution. The Royal Society of Chemistry 2020-11-27 /pmc/articles/PMC8179122/ /pubmed/34163903 http://dx.doi.org/10.1039/d0sc05327a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Mao, Yuezhi
Loipersberger, Matthias
Kron, Kareesa J.
Derrick, Jeffrey S.
Chang, Christopher J.
Sharada, Shaama Mallikarjun
Head-Gordon, Martin
Consistent inclusion of continuum solvation in energy decomposition analysis: theory and application to molecular CO(2) reduction catalysts
title Consistent inclusion of continuum solvation in energy decomposition analysis: theory and application to molecular CO(2) reduction catalysts
title_full Consistent inclusion of continuum solvation in energy decomposition analysis: theory and application to molecular CO(2) reduction catalysts
title_fullStr Consistent inclusion of continuum solvation in energy decomposition analysis: theory and application to molecular CO(2) reduction catalysts
title_full_unstemmed Consistent inclusion of continuum solvation in energy decomposition analysis: theory and application to molecular CO(2) reduction catalysts
title_short Consistent inclusion of continuum solvation in energy decomposition analysis: theory and application to molecular CO(2) reduction catalysts
title_sort consistent inclusion of continuum solvation in energy decomposition analysis: theory and application to molecular co(2) reduction catalysts
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179122/
https://www.ncbi.nlm.nih.gov/pubmed/34163903
http://dx.doi.org/10.1039/d0sc05327a
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