Transition‐state optimization on free energy surface: Toward solution chemical reaction ergodography
Transition‐state optimization on free energy surface: Toward solution chemical reaction ergodography
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自由能表面上的过渡态优化：面向溶液化学反应遍历图
DOI：
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
T. Yamabe
中科院分区：
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作者：
Naoto Okuyama;M. Nagaoka;T. Yamabe
为了获得溶液化学反应的过渡态，提出了一种新的多维自由能曲面上的过渡态优化方法。类似于Born-Oppenheimer势能面的从头计算方法，该方法利用FES上的力和Hessian，可以通过分子动力学方法和自由能微扰理论计算。在此基础上，提出了FES上内禀反应坐标的定义。通过对计算量的估计和数值精度的比较，我们认为该方法比仅利用自由能的方法更有效。最后，讨论了TS优化和IRC在FES上应该成为非常重要的工具，以开发一个新的研究领域，称为溶液化学反应遍历。Int J Quant Chem 70：95-103，1998
To obtain a transition state (TS) in solution chemical reaction, a new TS optimization method has been proposed on a multidimensional free energy surface (FES). Analogous to the method for the Born–Oppenheimer potential energy surface using ab initio molecular orbital calculation, the present method utilizes force and Hessian on the FES, which can be calculated by molecular dynamics method and the free energy perturbation theory. Furthermore, on the basis of the method, we have proposed the definition of the intrinsic reaction coordinate (IRC) on the FES. According to not only the estimation of the computational demand but also the comparison of the numerical accuracy, we conclude that our method should be more efficient than such other methods that utilize only the free energy. Finally, it is discussed that the TS optimization and the IRC on the FES should become very important tools to develop a new research field called the solution chemical reaction ergodography. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 70: 95–103, 1998