从头算
丙烯
化学
氢甲酰化
反应速率常数
动能
计算化学
热力学
产量(工程)
量子
反应速率
动力学
催化作用
物理
铑
量子力学
有机化学
作者
Lifei Guo,Jeremy N. Harvey
标识
DOI:10.26434/chemrxiv-2023-b1wvh
摘要
Kinetic modelling of catalytic reaction systems can yield detailed insight into mechanisms, enabling in particular the identification of rate- and turnover-limiting steps. Empirical models fitted to observed kinetics do not always unambiguously resolve the microscopic nature of the mechanism, while ab initio models with rate constants derived from statistical rate theories and quantum chemistry invariably lead to mismatches between predicted and observed rates, sometimes even to the extent that the dependence of the rate on key variables such as temperature or concentration is incorrect. We have shown previously that when using accurate quantum chemical methods, agreement with experiment of ab initio kinetic models can be good, and can be further improved by performing limited fitting of the ab initio values. Here we show that a detailed assessment of the remaining mismatches with experiment combined with a careful fitting protocol and with additional quantum chemical calculations can yield much improved accuracy and improved microscopic understanding of the reaction mechanism, for the important test case of propene hydroformylation by Co2(CO)8.
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