The original version of the article contained erroneously derived values of C_G and related thermochemical constants in Table 1. C_G is the constant used to convert reduction potentials and pK_a values into bond dissociation free energies (BDFEs). The errors were due to an improper correction of the standard state for H^• in solution from unit mole fraction (χ = 1) to 1 molar. For a detailed description of the correct derivation, we refer readers to section S5 of our recent J. Am. Chem. Soc. article. (1) Reproduced below is a new version of Table 1 which includes corrected values of the thermochemical constants. The differences between the original and corrected C_G values (ΔC_G) are given in the second column of the table; the corrections range from 2 to 5 kcal mol^–1. Values in kcal mol^–1 at 298 K. ΔC_G = C_G^init – C_G where C_G^init is the value reported in the 2010 review. T(ΔS°)_solv = T[ΔS°(H^•)_g + ΔS_solvation°(H₂)_solv], where _g indicates gas phase and _solv indicates a solvated species. Unfortunately, since these thermochemical constants were used to derive nearly every value in the subsequent tables of the original manuscript, the reported values were typically systematically in error by several kcal mol^–1. While this change affects the absolute reported values, it does not change the accuracy of the relative values reported in the same solvent. Due to the extent of this correction, we have chosen to provide a new version of the 2010 Chemical Review with completely revised tables (ref (7)). This new version details the thermochemical cycles used to derive all values, as well as advancements in the field of PCET thermochemistry over the past decade, and discussions of emerging areas where it has or will become of import. We apologize for any inconvenience to authors who used the incorrect values in our original review, and we hope that our thorough and transparent update will serve as an improved guide to this area. (7) We acknowledge the help of Sergei Lymar of Brookhaven National Laboratory, who originally pointed out our thermochemical errors, and especially the help and insights of Eric S. Wiedner, Aaron M. Appel, and Morris Bullock of Pacific Northwest National Laboratory for their helpful discussions. This work was primarily supported as part of the Center for Molecular Electrocatalysis (CME), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. R.G.A. gratefully acknowledges support from a National Science Foundation Graduate Research Fellowship. This article references 7 other publications.

中文翻译：

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质子耦合电子转移试剂热化学的修正及其意义

表 1 中文章的原始版本包含错误导出的C _{G值和相关热化学常数}。C _G是用于将还原电势和 p K _a值转换为键解离自由能 (BDFE) 的常数。这些错误是由于溶液中H ^{• 的}标准状态从单位摩尔分数(χ = 1) 到1 摩尔的修正不当造成的。对于正确推导的详细描述，我们建议读者参阅我们最近发表的J. Am. 的 S5 节。化学。苏克。文章。(1) 下面复制的是表 1 的新版本，其中包括热化学常数的修正值。原始C _G值与校正 C G 值之间的差异(Δ C _G ) 在表的第二列中给出；修正范围为 2 至 5 kcal mol ^–1。298 K 时的值以 kcal mol ^{–1为单位。 Δ} C _G = C _G ^init – C _G其中C _G ^init是 2010 年审查中报告的值。T (Δ S °) _solv = T [Δ S °(H ^• ) _g + Δ S_溶剂化°(H ₂ ) _solv ]，其中_g表示气相，_solv表示溶剂化物质。不幸的是，由于这些热化学常数被用来推导原始手稿后续表格中的几乎所有值，因此报告的值通常有几个 kcal mol ^–1的系统误差。虽然这种变化影响绝对报告值，但它不会改变同一溶剂中报告的相对值的准确性。由于此更正的范围，我们选择提供 2010 年化学评论的新版本，其中包含完全修订的表格（参考文献 (7)）。这个新版本详细介绍了用于推导所有值的热化学循环，以及过去十年 PCET 热化学领域的进展，以及对其已经或将变得重要的新兴领域的讨论。对于在我们的原始评论中使用错误值的作者造成的任何不便，我们深表歉意，我们希望我们彻底和透明的更新将成为该领域的改进指南。(7)我们感谢布鲁克海文国家实验室的 Sergei Lymar 的帮助，他最初指出了我们的热化学错误，特别感谢太平洋西北国家实验室的 Eric S. Wiedner、Aaron M. Appel 和 Morris Bullock 的帮助和见解，他们进行了有益的讨论。这项工作主要得到分子电催化中心 (CME) 的支持，该中心是一个由美国能源部、科学办公室、基础能源科学办公室资助的能源前沿研究中心。RGA 衷心感谢国家科学基金会研究生研究奖学金的支持。本文参考了其他 7 篇出版物。