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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...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2020
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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. |
format | Online Article Text |
id | pubmed-8179122 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
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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