The kinetics of many reactions are critically dependent upon the barrier heights for which accurate determination can be difficult. From the perspective of attaining such quantities using computational quantum chemistry, it is important to appropriately validate routine and efficient methodologies such as density functional theory (DFT) procedures. In the present study, we embark on the journey of establishing diverse databases using a consistent high-level quantum chemistry procedure, against which new and existing methodologies can be assessed. Thus, we have used the composite protocol W3X-L to provide more than 100 refined reference values for existing databases [e.g., Y. Zhao and D. G. Truhlar, J. Phys. Chem. A, 2005, 109, 5656] and additionally establish benchmark data that are of interest to atmospheric and combustion chemists. While our endeavor has just begun, assessment of various DFT methods with our existing results lends support to the use of MN15 as an adequate method for general kinetics applications. We also recommend the use of less-costly W2X and WG composite protocols for obtaining adequately accurate reference thermochemical values for larger molecular systems.

中文翻译：

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气压计–气相反应精确势垒高度的增强数据库†

许多反应的动力学关键取决于势垒高度，对于这些势垒高度很难准确确定。从使用计算量子化学获得此类数量的角度来看，适当验证常规且有效的方法（例如密度泛函理论（DFT）程序）非常重要。在本研究中，我们开始使用一致的高级量子化学程序建立各种数据库的过程，以此可以评估新方法和现有方法。因此，我们已经使用复合协议W3X-L为现有数据库提供了100多个精炼参考值[例如，Y。Zhao和DG Truhlar，J。Phys 。化学 A，2005，109（5656），并另外建立大气和燃烧化学家感兴趣的基准数据。尽管我们的工作才刚刚开始，但根据现有结果对各种DFT方法进行评估，就可以支持将MN15用作一般动力学应用的适当方法。我们还建议使用成本较低的W2X和WG复合规程，以获取较大分子系统的足够准确的参考热化学值。