In this work, we propose a cost-effective protocol for the calculation of rate constants within the framework of multiconformer transition state theory. We have developed this methodology while calculating for the first time on a theoretical level rate constants for a series of six reactions between the OH radical and hydrofluoropolyethers: the latter are promising third-generation CFC replacements whose atmospheric impact is still widely unknown. Our investigation, which is based on computationally accessible M08-HX/apcseg-2//M08-HX/pcseg-1 calculations, shows that two of our rate constants are within a factor of 0.6 and 1.4 of experimental data, a good result that probably benefits from some error cancellation. It also exhibits a reactivity trend, for which we provide detailed insights that could be used to shed new light on the general reactivity of ethers toward OH. Finally, because the studied reactions share a ubiquitous mechanism in atmospheric chemistry, we hope that our protocol can be routinely applied to explore the reactivity of computationally challenging reactions and to pave new ways in the development of greener CFC replacements.

中文翻译：

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通过一种经济有效的协议来研究氢氟聚醚对OH的反应性，以计算多构象过渡态理论速率常数

在这项工作中，我们提出了一种经济高效的协议，用于在多conformer过渡状态理论的框架内计算速率常数。我们已经开发出了这种方法，同时首次根据理论水平的速率常数计算了OH自由基与氢氟聚醚之间的一系列六个反应：后者是有希望的第三代CFC替代品，其对大气的影响仍然广为人知。我们的研究基于可计算访问的M08-HX / apcseg-2 // M08-HX / pcseg-1计算，结果表明我们的两个速率常数在实验数据的0.6和1.4范围内，这是一个很好的结果可能受益于一些错误消除。它也表现出反应性趋势，为此，我们提供了详细的见解，可用于阐明醚对OH的一般反应性。最后，由于所研究的反应在大气化学中具有普遍存在的机制，因此我们希望我们的方案可以常规应用，以探索计算难度较大的反应的反应性，并为开发更环保的CFC替代品铺平新的途径。