Explicitly Unraveling the Roles of Counterions, Solvent Molecules, and Electron Correlation in Solution Phase Reaction Pathways
| Autor: | Mitchell C. Groenenboom, John A. Keith |
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| Rok vydání: | 2016 |
| Předmět: |
Work (thermodynamics)
Aqueous solution 010304 chemical physics Electronic correlation Chemistry Implicit solvation Solvation 010402 general chemistry 01 natural sciences Quantum chemistry 0104 chemical sciences Surfaces Coatings and Films Molecular dynamics Computational chemistry Chemical physics 0103 physical sciences Materials Chemistry Periodic boundary conditions Physics::Chemical Physics Physical and Theoretical Chemistry |
| Zdroj: | The Journal of Physical Chemistry B. 120:10797-10807 |
| ISSN: | 1520-5207 1520-6106 |
| DOI: | 10.1021/acs.jpcb.6b07606 |
| Popis: | Studies utilizing continuum solvation methods can sometimes omit critically important solute–solvent interactions, while explicitly sampling full solution phase mechanisms accurately with Born–Oppenheimer molecular dynamics (BOMD) is computationally costly. In this work, we benchmark components for an alternative IRCMax-like procedure for refined analyses of electronic energies along reaction pathways. The procedure involves obtaining molecular clusters from nudged elastic band calculations for use in mixed explicit-continuum models. The reaction energetics from these models correspond well to energetics obtained from explicit models using periodic boundary conditions, and the clusters obtained are more amenable to treatments with high levels of quantum chemistry theory. We demonstrate this approach using CO2 reduction by NaBH4 and NaBH3OH in aqueous solution as test cases. We show that the local solvation environment containing explicit solvent molecules and a counterion within the entire first solvation... |
| Databáze: | OpenAIRE |
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