Computational Electrochemistry: The Aqueous Ru<sup>3+</sup>|Ru<sup>2+</sup> Reduction Potential

Jaque, Pablo; Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.

doi:10.1021/jp066765w

Cited by 133 publications

(170 citation statements)

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“…In general, basis sets such as the double or triple zeta basis with additional diffuse and polarization functions are sufficient to capture the energetics of redox processes [60,61]. Since the redox process may lead to anionic species, diffuse functions are crucial to smear the electron density over the space.…”

Section: Basis Set Choicementioning

confidence: 99%

“…Explicit solvation by adding explicit water molecules around the solute can describe the hydrogen bonding environment more accurately [60,79] than a pure dielectric fluid approach. However, this method is computationally expensive, and therefore less commonly used because the CPCM solvation captures the solvation process comparatively well.…”

Section: Solvationmentioning

confidence: 99%

“…However, this method is computationally expensive, and therefore less commonly used because the CPCM solvation captures the solvation process comparatively well. The standard reduction potential for Ru(3+/2+) aqueous redox couple was examined using 37 DFT functionals with five different basis sets and the solvation effects were modeled using the SM6 solvation model [60]. In addition, the effect of the second hydration shell on the predicted standard reduction potential was investigated.…”

Section: Solvationmentioning

confidence: 99%

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Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Arumugam

Becker

2014

Minerals

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Abstract:Applications of redox processes range over a number of scientific fields. This review article summarizes the theory behind the calculation of redox potentials in solution for species such as organic compounds, inorganic complexes, actinides, battery materials, and mineral surface-bound-species. Different computational approaches to predict and determine redox potentials of electron transitions are discussed along with their respective pros and cons for the prediction of redox potentials. Subsequently, recommendations are made for certain necessary computational settings required for accurate calculation of redox potentials. This article reviews the importance of computational parameters, such as basis sets, density functional theory (DFT) functionals, and relativistic approaches and the role that physicochemical processes play on the shift of redox potentials, such as hydration or spin orbit coupling, and will aid in finding suitable combinations of approaches for different chemical and geochemical applications. Identifying cost-effective and credible computational approaches is essential to benchmark redox potential calculations against experiments. Once a good theoretical approach is found to model the chemistry and thermodynamics of the redox and electron transfer process, this knowledge can be incorporated into models of more complex reaction mechanisms that include diffusion in the solute, surface diffusion, and dehydration, to name a few. This knowledge is important to fully understand the nature of redox processes be it a geochemical process that dictates natural redox reactions or one that is being used for the optimization of a chemical process in industry. In addition, it will help identify materials that will be useful to design catalytic OPEN ACCESSMinerals 2014, 4 346 redox agents, to come up with materials to be used for batteries and photovoltaic processes, and to identify new and improved remediation strategies in environmental engineering, for example the reduction of actinides and their subsequent immobilization. Highly under-investigated is the role of redox-active semiconducting mineral surfaces as catalysts for promoting natural redox processes. Such knowledge is crucial to derive process-oriented mechanisms, kinetics, and rate laws for inorganic and organic redox processes in nature. In addition, molecular-level details still need to be explored and understood to plan for safer disposal of hazardous materials. In light of this, we include new research on the effect of iron-sulfide mineral surfaces, such as pyrite and mackinawite, on the redox chemistry of actinyl aqua complexes in aqueous solution.

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Section: Basis Set Choicementioning

confidence: 99%

Section: Solvationmentioning

confidence: 99%

Section: Solvationmentioning

confidence: 99%

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Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Arumugam

Becker

2014

Minerals

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“…Formation. Accumulated experimental and theoretical studies (11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29) on artificial photosynthesis systems have elucidated dual possible mechanisms of the water splitting reaction: (i) the radical coupling (RC) mechanism and (ii) the acid-base mechanism. Tanaka and coworkers have proposed the former mechanism for the water splitting reaction by their Ru-quinone complexes as illustrated in Fig.…”

Section: Possible Electronic and Spin States Of Mononuclear And Binucmentioning

confidence: 99%

“…In the past decades, a number of experimental and theoretical studies (11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29) have been performed to design artificial photosynthetic systems that mimic native PSII systems. Many binuclear transition-metal catalysts such as LðH 2 OÞM-O-MðOH 2 ÞL or LðH 2 OÞM-BL-MðOH 2 Þ (where L and BL are nonbridging and bridging organic ligands, respectively) were prepared and characterized for their catalytic properties toward water oxidation (11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21).…”

mentioning

confidence: 99%

Similarities of artificial photosystems by ruthenium oxo complexes and native water splitting systems

Tanaka

Isobe

Yamanaka

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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The nature of chemical bonds of ruthenium(Ru)-quinine(Q) complexes, mononuclear ½RuðtrpyÞð3,5-t-Bu 2 QÞðOH 2 Þ ðClO 4 Þ 2 (trpy ¼ 2,2 0 : 6 0 ,2 0 0 -terpyridine, 3,5-di-tert-butyl-1,2-benzoquinone) (1), and binuclear ½Ru 2 ðbtpyanÞð3,6-di-Bu 2 QÞ 2 ðOH 2 Þ 2þ ðbtpyan ¼ 1,8-bisð2,2 0 : 6 0 ,2 0 0 -terpyrid-4 0 -ylÞanthracene, 3,6-t-Bu 2 Q ¼ 3,6-di-tertbutyl-1,2-benzoquinone) (2), has been investigated by broken-symmetry (BS) hybrid density functional (DFT) methods. BS DFT computations for the Ru complexes have elucidated that the closed-shell structure (2b) Ru(II)-Q complex is less stable than the open-shell structure (2bb) consisting of Ru(III) and semiquinone (SQ) radical fragments. These computations have also elucidated eight different electronic and spin structures of tetraradical intermediates that may be generated in the course of water splitting reaction. The Heisenberg spin Hamiltonian model for these species has been derived to elucidate six different effective exchange interactions (J) for four spin systems. Six J values have been determined using total energies of the eight (or seven) BS solutions for different spin configurations. The natural orbital analyses of these BS DFTsolutions have also been performed in order to obtain natural orbitals and their occupation numbers, which are useful for the lucid understanding of the nature of chemical bonds of the Ru complexes. Implications of the computational results are discussed in relation to the proposed reaction mechanisms of water splitting reaction in artificial photosynthesis systems and the similarity between artificial and native water splitting systems.four redox center | manganese clusters | water oxidation | oxyl radical | O-O bond formation P hotosynthesis is one of the most important chemical processes on our planet. Extensive experimental studies (1-6) on the process have revealed that oxygenic photosynthesis involves several protein-cofactor complexes embedded in the photosynthetic thylakoid membranes of plants, green algae, and cyanobacteria. Among these complexes, photosystem II (PSII) has a prominent role because it catalyzes the oxidation of water (, which is the prerequisite for all aerobic life. The main cyclic process to catalyze the water-oxidation consists of successive four steps, which is referred to as the Kok cycle (6). During this process, the oxygen-evolving complex (OEC), the catalyst of the water oxidation reaction, takes five oxidation states (S 0 -S 4 ). The OEC in PSII contains an inorganic cluster consisting of four manganese ions and one calcium ion that are bridged by at least five oxygens; the active site is therefore expressed with the CaMn 4 O 5 cluster (3) (5). Very recently, the electronic structure and reactivity of 3 (7-10) have been elucidated based on the new high-resolution X-ray structure (5).In the past decades, a number of experimental and theoretical studies (11-29) have been performed to design artificial photosynthetic systems that mimic native PSII systems. Many binuclear transition-metal catalysts s...

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Theory of Ferrocenyl Compounds

Derat

Costuas

Volatron

2012

Patai's Chemistry of Functional Groups

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The aim of this chapter is to introduce the basic knowledge necessary to understand the electronic structure of ferrocenyl compounds. Molecular orbitals analysis is presented first, followed by a more contemporary description by density functional theory or elaborated ab initio calculations. In order to correlate computational results with experimental data, recent theoretical analysis of vibrational and Mössbauer spectroscopy, redox and excited states, are summarized. Due to numerous applications in non‐linear optics, calculated properties of ferrocenyl compounds in this field are presented. Catalytic and biological processes involving derivatives of ferrocenyl compounds have been studied from a theoretical point of view and are reviewed here. Ferrocenyl compounds are often used as a building block for constructing bigger chemical systems; simulation of large systems is a challenge, especially when involving metallic compounds. Nevertheless, some theoretical studies hav been done in that field (e.g. nanoparticles decorated with ferrocene or ferrocenyl compounds grafted onto gold surfaces) and are discussed in this chapter.

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Computational Electrochemistry: The Aqueous Ru³⁺|Ru²⁺ Reduction Potential

Cited by 133 publications

References 114 publications

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Similarities of artificial photosystems by ruthenium oxo complexes and native water splitting systems

Theory of Ferrocenyl Compounds

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Computational Electrochemistry: The Aqueous Ru3+|Ru2+ Reduction Potential

Cited by 133 publications

References 114 publications

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Similarities of artificial photosystems by ruthenium oxo complexes and native water splitting systems

Theory of Ferrocenyl Compounds

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Computational Electrochemistry: The Aqueous Ru³⁺|Ru²⁺ Reduction Potential