Reducing Systematic Uncertainty in Computed Redox Potentials for Aqueous Transition-Metal-Substituted Polyoxotungstates.
Reducing Systematic Uncertainty in Computed Redox Potentials for Aqueous Transition-Metal-Substituted Polyoxotungstates.
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DOI：
10.1021/acs.inorgchem.3c01115
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发表时间：
2023-08-07
影响因子：
4.6
通讯作者：
Vila-Nadal, Laia
中科院分区：
文献类型：
--
作者：
Thompson, Jake A.;Gonzalez-Cabaleiro, Rebeca;Vila-Nadal, Laia
聚氧乙烯酸酯由于其结构多样性、氧化还原稳定性和纳米级的功能性而引起了人们的极大兴趣。在这项工作中，密度泛函理论计算已被用来系统地研究各种交换相关泛函在再现实验氧化还原电位的准确性，在[PW 11 M（H2O）O39]q− M = Mn（III/II），Fe（III/II），Co（III/II），和Ru（III/II）中的U 0 Red。[PW 11 M（H2O）O39]q−的U 0 Red计算使用类似导体的屏蔽模型来中和团簇中的电荷。我们明确地定位了K+反离子，其诱导电位正移> 500 mV。这种近似改善了Kx[XW 11 M（H2O）O39]q-x M = Mn（III/II）/Co（III/II）的氧化还原电位的再现。然而，Kx[PW 11 M（H2O）O39]q−x M = Fe（III/II）/Ru（III/II）的U 0 Red的不确定性被观察到，因为离子对的过度稳定。不建议使用超过25% Hartree-Fock交换的混合泛函，因为Δ U 0 Red的不确定性很大，这归因于离子对的过度接近。我们的研究结果强调，了解电极和电解质环境的性质是必不可少的，以获得一个合理的理论和实验结果之间的协议。密度泛函理论计算已被用来评估交换相关泛函在重现实验氧化还原电位时的准确性，[PW 11 M（H2O）O39]q− M = Mn（III/II），Fe（III/II），Co（III/II），and Ru（III/II）中的U 0 Red。此外，我们已经明确定位了（K+）抗衡离子，使我们的系统的电荷中性形成Kx[XW 11 M（H2O）O39]q−x（x = 4或5），并评估了计算的U 0 Red值的影响。
Polyoxometalates have attracted significant interest owing to their structural diversity, redox stability, and functionality at the nanoscale. In this work, density functional theory calculations have been employed to systematically study the accuracy of various exchange–correlation functionals in reproducing experimental redox potentials, U0Red in [PW11M(H2O)O39]q− M = Mn(III/II), Fe(III/II), Co(III/II), and Ru(III/II). U0Red calculations for [PW11M(H2O)O39]q− were calculated using a conductor-like screening model to neutralize the charge in the cluster. We explicitly located K+ counterions which induced positive shifting of potentials by > 500 mV. This approximation improved the reproduction of redox potentials for Kx[XW11M(H2O)O39]q−x M = Mn(III/II)/Co(III/II). However, uncertainties in U0Red for Kx[PW11M(H2O)O39]q−x M = Fe(III/II)/Ru(III/II) were observed because of the over-stabilization of the ion-pairs. Hybrid functionals exceeding 25% Hartree–Fock exchange are not recommended because of large uncertainties in ΔU0Red attributed to exaggerated proximity of the ion-pairs. Our results emphasize that understanding the nature of the electrode and electrolyte environment is essential to obtain a reasonable agreement between theoretical and experimental results. Density functional theory calculations have been employed to assess the accuracy of exchange−correlation functionals in reproducing experimental redox potentials, U0Red in [PW11M(H2O)O39]q− M = Mn(III/II), Fe(III/II), Co(III/II), and Ru(III/II). Furthermore, we have explicitly located (K+) counterions, rendering our systems’ charge neutral forming Kx[XW11M(H2O)O39]q−x (x = 4 or 5) and assessing the effect of computed U0Red values.
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影响因子：
15
作者：
López, X;Maestre, JM;Poblet, JM
通讯作者：
Poblet, JM
影响因子：
64.8
作者：
Busche, Christoph;Vila-Nadal, Laia;Cronin, Leroy
通讯作者：
Cronin, Leroy
影响因子：
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作者：
Kuznetsova, NI;Kuznetsova, LI;Likholobov, VA
通讯作者：
Likholobov, VA
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
影响因子：
15
作者：
LYON, DK;MILLER, WK;FINKE, RG
通讯作者：
FINKE, RG