Au nanoclusters (Au NCs) stabilized by poly(N‐vinyl‐2‐pyrrolidone) and poly(allylamine), abbreviated to Au:PVP and Au:PAA, catalyze the aerobic oxidation of p‐hydroxybenzyl alcohols, but the catalytic activity of Au:PVP is much higher than that of Au:PAA. To elucidate the correlations between the catalytic activities and coordination structures of the stabilizing polymer, the substrate accessibility on Au NCs was estimated by density functional theory (DFT) and molecular dynamics (MD) calculations. For MD simulations, we applied a systematic method to optimize the temperature parameters in temperature replica exchange molecular dynamics (T‐REMD), and the coordination structures were comprehensively classified by multivariate analysis. The results show that the number of open active sites on the Au NCs is a good index for predicting the catalytic activities. © 2018 Wiley Periodicals, Inc.

中文翻译：

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聚合物稳定的au纳米团簇催化剂配位结构与催化活性相关性的理论研究

由聚（N-乙烯基-2-吡咯烷酮）和聚（烯丙胺）稳定的 Au 纳米团簇（Au NCs），缩写为 Au:PVP 和 Au:PAA，催化对羟基苯甲醇的有氧氧化，但 Au 的催化活性:PVP 远高于 Au:PAA。为了阐明催化活性与稳定聚合物的配位结构之间的相关性，通过密度泛函理论 (DFT) 和分子动力学 (MD) 计算估算了 Au NCs 上的底物可及性。对于MD模拟，我们应用系统方法优化温度副本交换分子动力学（T-REMD）中的温度参数，并通过多元分析对配位结构进行综合分类。结果表明，Au NCs 上开放活性位点的数量是预测催化活性的良好指标。© 2018 Wiley Periodicals, Inc.