Iioka Tatsuya, Takahashi Satoshi, Yoshida Yuichiro, Matsumura Yoshihiro, Hiraoka Shuichi, Sato Hirofumi
Department of Molecular Engineering, Kyoto University, Kyoto 615-8510, Japan.
Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo 153-8902, Japan.
J Comput Chem. 2019 Jan 5;40(1):279-285. doi: 10.1002/jcc.25588. Epub 2018 Oct 9.
The kinetics on a basic ligand substitution reaction on dinuclear platinum complexes [Pt(PEt ) PhPt(PEt ) ] and [Pt(PEt ) PhCOPhPt(PEt ) ] , with the ligands pyridine and 3-chloropyridine, is studied. This is a fundamental step in a self-assembly, and the time evolution has been observed with a new experimental technique, QASAP (quantitative analysis of self-assembly process), which is recently developed by Hiraoka's group. As a result of numerical calculations based on master equation, we succeed in specifying the reaction rate constants with a simple reaction model. In addition, the time evolutions of all the intermediate components produced and consumed in chemical reaction are revealed, including those unobserved in the experiments. The convergence behavior of the existence ratios of specific chemical species calculated with the stochastic algorithm method is compared with those obtained from deterministic formalism based on rate equations, revealing a clear dependence on the number of constituent molecules. © 2018 Wiley Periodicals, Inc.
研究了双核铂配合物[Pt(PEt ) PhPt(PEt ) ]和[Pt(PEt ) PhCOPhPt(PEt ) ]与配体吡啶和3-氯吡啶发生的碱性配体取代反应的动力学。这是自组装过程中的一个基本步骤，采用平冈小组最近开发的一种新实验技术QASAP（自组装过程定量分析）观测了时间演化。基于主方程进行数值计算的结果是，我们成功地用一个简单的反应模型确定了反应速率常数。此外，还揭示了化学反应中产生和消耗的所有中间组分的时间演化，包括实验中未观测到的那些组分。将用随机算法方法计算的特定化学物种存在比的收敛行为与基于速率方程的确定性形式得到的结果进行了比较，揭示了其对组成分子数量的明显依赖性。© 2018威利期刊公司
