Development of Reaction Density Functional Theory and Its Application to Glycine Tautomerization Reaction in Aqueous Solution
Development of Reaction Density Functional Theory and Its Application to Glycine Tautomerization Reaction in Aqueous Solution
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DOI：
10.1021/acs.jpcc.8b05383
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发表时间：
2018-08
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影响因子：
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通讯作者：
Weiqiang Tang;Cheng Cai;Shuangliang Zhao;Honglai Liu
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文献类型：
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作者：
Weiqiang Tang;Cheng Cai;Shuangliang Zhao;Honglai Liu
反应能垒的准确确定是化学反应工程中的关键，它直接关系到反应速率和反应路径，而大量的量子计算依赖于商业软件已经被报道用于理解反应机理，溶剂对反应能垒的影响仍然知之甚少。困难部分源于反应位点周围不均匀溶剂结构的捕获不良。在这里，我们提出了一个反应密度泛函理论（RxDFT）相结合的量子密度泛函理论计算内禀反应能与经典的密度泛函理论解决溶剂化的贡献。为了演示，甘氨酸在水溶液中的互变异构反应，重新使用RxDFT。我们说明，两个不同的反应路径的自由能分布可以很好地预测，与分子动力学/MP2模拟的结果相比。由于没有溶剂分子I.
Accurate determination of reaction barrier is crucial in chemical reaction engineering since it is directly associated with the reaction rate and reaction path. Whereas massive quantum calculations relying on commercial software have been reported for understanding reaction mechanisms, the solvent effect on the reaction barrier is still poorly understood. The difficulty originates partially from the ill capture of the inhomogeneous solvent structure around the reaction site. Herein, we propose a reaction density functional theory (RxDFT) by combining the quantum density functional theory for calculating intrinsic reaction energy with the classical density functional theory for addressing solvation contribution. For demonstration, the glycine tautomerization reaction in aqueous solution is revisited by using RxDFT. We illustrate that the free energy profiles of two distinct reaction paths can be well predicted, in comparison with the results of molecular dynamics/MP2 simulation. Since no solvent molecule i...