Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high‐accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero‐ and infinite‐pressure limits; (c) a hindered‐rotor model for HOCO that implicitly includes the cis‐ and trans‐conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty.

中文翻译：

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HO + CO的半经典过渡态理论/主方程动力学：性能评估

以前，使用半经典跃迁状态理论（SCTST）和高精度外推从头算热化学（HEAT）进行的主方程（ME）模拟预测的速率常数与已公布的实验数据在宽广的压力和温度（≳250K）下均极佳地相符，但是该协议在较低温度下效果不佳。通过（a）严格评估已发布的实验数据并进行调查，研究了性能降低的可能原因；（b）三种不同的角动量的ME处理，包括一种在零压力和无限压力极限处精确处理的方法；（c）HOCO的受阻转子模型隐含了顺式和反式构象异构体；（d）对热化学的可能的经验调整；（e）对虚构的频率控制隧穿进行可能的经验调整；（f）包括或忽略反应前配合物PRC1；（g）其可能的双分子反应。改进包括更好地近似SCTST中的因子，以及使用Hill和van Vleck处理角动量耦合。对文献数据的评估并没有发现任何具体的缺陷，但是所陈述的不确定性可能会被低估。所有ME处理都非常适合以下实验数据Ť ≥250 K，但在差异Ť  <为250K存在。请注意，每个ME模型都需要单独的经验能量传递参数。热化学调节无法匹配实验H / D动力学同位素效应。调整假想频率可以达到良好的拟合度，但是调整幅度过大。是否包括PRC1及其可能的双分子反应几乎没有影响。我们得出的结论是，任何调整都不是对未调整理论的改进。注意，与理论上的差异范围内仅存在一组实验数据，而DO + CO的数据很少。