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Redox Potentials from Ab Initio Molecular Dynamics and Explicit Entropy Calculations: Application to Transition Metals in Aqueous Solution
dc.creator | Caro M.A. | spa |
dc.creator | Lopez-Acevedo O. | spa |
dc.creator | Laurila T. | spa |
dc.date.accessioned | 2017-12-19T19:36:41Z | |
dc.date.available | 2017-12-19T19:36:41Z | |
dc.date.created | 2017 | |
dc.identifier.issn | 15499618 | |
dc.identifier.uri | http://hdl.handle.net/11407/4253 | |
dc.description.abstract | We present a complete methodology to consistently estimate redox potentials strictly from first-principles, without any experimental input. The methodology is based on (i) ab initio molecular dynamics (MD) simulations, (ii) all-atom explicit solvation, (iii) the two-phase thermodynamic (2PT) model, and (iv) the use of electrostatic potentials as references for the absolute electrochemical scale. We apply the approach presented to compute reduction potentials of the following redox couples: Cr2+/3+, V2+/3+, Ru(NH3)62+/3+, Sn2+/4+, Cu1+/2+, FcMeOH0/1+, and Fe2+/3+ (in aqueous solution) and Fc0/1+ (in acetonitrile). We argue that fully quantum-mechanical simulations are required to correctly model the intricate dynamical effects of the charged complexes on the surrounding solvent molecules within the solvation shell. Using the proposed methodology allows for a computationally efficient and statistically stable approach to compute free energy differences, yielding excellent agreement between our computed redox potentials and the experimental references. The root-mean-square deviation with respect to experiment for the aqueous test set and the two exchange-correlation density functionals used, PBE and PBE with van der Waals corrections, are 0.659 and 0.457 V, respectively. At this level of theory, depending on the functional employed, its ability to correctly describe each particular molecular complex seems to be the factor limiting the accuracy of the calculations. © 2017 American Chemical Society. | eng |
dc.language.iso | eng | |
dc.publisher | American Chemical Society | spa |
dc.relation.isversionof | https://www.scopus.com/inward/record.uri?eid=2-s2.0-85027228601&doi=10.1021%2facs.jctc.7b00314&partnerID=40&md5=e934b462e00f989f9f4e16ce4500392c | spa |
dc.source | Scopus | spa |
dc.title | Redox Potentials from Ab Initio Molecular Dynamics and Explicit Entropy Calculations: Application to Transition Metals in Aqueous Solution | spa |
dc.type | Article | eng |
dc.rights.accessrights | info:eu-repo/semantics/restrictedAccess | |
dc.contributor.affiliation | Caro, M.A., Department of Electrical Engineering and Automation, Aalto University, Espoo, Finland, COMP Centre of Excellence in Computational Nanoscience, Department of Applied Physics, Aalto University, Espoo, Finland | spa |
dc.contributor.affiliation | Lopez-Acevedo, O., COMP Centre of Excellence in Computational Nanoscience, Department of Applied Physics, Aalto University, Espoo, Finland, Departamento de Facultad de Ciencias Básicas, Universidad de Medellín, Medellín, Colombia | spa |
dc.contributor.affiliation | Laurila, T., Department of Electrical Engineering and Automation, Aalto University, Espoo, Finland | spa |
dc.identifier.doi | 10.1021/acs.jctc.7b00314 | |
dc.publisher.faculty | Facultad de Ciencias Básicas | spa |
dc.abstract | We present a complete methodology to consistently estimate redox potentials strictly from first-principles, without any experimental input. The methodology is based on (i) ab initio molecular dynamics (MD) simulations, (ii) all-atom explicit solvation, (iii) the two-phase thermodynamic (2PT) model, and (iv) the use of electrostatic potentials as references for the absolute electrochemical scale. We apply the approach presented to compute reduction potentials of the following redox couples: Cr2+/3+, V2+/3+, Ru(NH3)62+/3+, Sn2+/4+, Cu1+/2+, FcMeOH0/1+, and Fe2+/3+ (in aqueous solution) and Fc0/1+ (in acetonitrile). We argue that fully quantum-mechanical simulations are required to correctly model the intricate dynamical effects of the charged complexes on the surrounding solvent molecules within the solvation shell. Using the proposed methodology allows for a computationally efficient and statistically stable approach to compute free energy differences, yielding excellent agreement between our computed redox potentials and the experimental references. The root-mean-square deviation with respect to experiment for the aqueous test set and the two exchange-correlation density functionals used, PBE and PBE with van der Waals corrections, are 0.659 and 0.457 V, respectively. At this level of theory, depending on the functional employed, its ability to correctly describe each particular molecular complex seems to be the factor limiting the accuracy of the calculations. © 2017 American Chemical Society. | eng |
dc.creator.affiliation | Department of Electrical Engineering and Automation, Aalto University, Espoo, Finland | spa |
dc.creator.affiliation | COMP Centre of Excellence in Computational Nanoscience, Department of Applied Physics, Aalto University, Espoo, Finland | spa |
dc.creator.affiliation | Departamento de Facultad de Ciencias Básicas, Universidad de Medellín, Medellín, Colombia | spa |
dc.relation.ispartofes | Journal of Chemical Theory and Computation | spa |
dc.relation.ispartofes | Journal of Chemical Theory and Computation Volume 13, Issue 8, 8 August 2017, Pages 3432-3441 | spa |
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dc.type.version | info:eu-repo/semantics/publishedVersion | |
dc.type.driver | info:eu-repo/semantics/article | |
dc.identifier.reponame | reponame:Repositorio Institucional Universidad de Medellín | spa |
dc.identifier.instname | instname:Universidad de Medellín | spa |
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