Quantum Mechanical Modeling of Reaction Rate Acceleration in Microdroplets
Quantum Mechanical Modeling of Reaction Rate Acceleration in Microdroplets
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DOI：
10.1021/acs.jpca.0c03225
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发表时间：
2020-06-18
影响因子：
2.9
通讯作者：
Kubis, Tillmann
中科院分区：
文献类型：
--
作者：
Narendra, Namita;Chen, Xingshuo;Kubis, Tillmann
微滴中的有机反应可能比大液滴中的有机反应快几个数量级。我们假设体相和界面之间的溶剂化能差对本征速率常数的增加起着关键作用，并用显式溶剂计算验证了这一假设。对于质子化的苯肼试剂和肼过渡态(TSB)，我们都证明了将电荷位置放置在表面的分子取向提供了高能量。这种高能形式转变为完全溶剂化TSB的途径比体相的活化能低约59kJ/mol，这一结果与实验的速率加速研究一致。
Organic reactions in microdroplets can be orders of magnitude faster than their bulk counterparts. We hypothesize that solvation energy differences between bulk and interface play a key role in the intrinsic rate constant increase and test the hypothesis with explicit solvent calculations. We demonstrate for both the protonated phenylhydrazine reagent and the hydrazone transition state (TSB) that molecular orientations which place the charge sites at the surface confer high energy. A pathway in which this high-energy form transforms into a fully solvated TSB has a lower activation energy than bulk by some 59 kJ/mol, a result that is consistent with experimental rate acceleration studies.