Rate constants have been measured for the removal of OH(v= 0), OD(v= 0), OH(v= 1) and OD(v= 1) in collisions with CO. At room temperature (298 ± 4 K) and in 18 or 25 Torr argon, the values obtained were (k/10^–13 cm³ molecule^–1 s^–1)= 1.53 ± 0.15, 0.55 ± 0.1, 10 ± 2 and 9.5 ± 2, respectively. Our results for OH(v= 0) and OD(v= 0) agree well with those of other workers. The previously undetermined rate constants for OH(v= 1) and OD(v= 1) with CO are believed to correspond to those for formation of an (HOCO) adduct which can decompose either to H + CO₂ or back to OH + CO, but with vibrational relaxation of the OH. Based on this proposition, transition-state theory calculations have been performed on the elementary processes which occur when OH, OD and CO collide. The calculations successfully explain the values of the rate constants in these systems and their dependence on temperature, pressure, isotopic substitution and reagent excitation.

中文翻译：

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OH（v = 0，1）和OD（v = 0，1）与CO的动力学以及OH + CO反应的机理

已测量了与CO碰撞时去除OH（v = 0），OD（v = 0），OH（v = 1）和OD（v = 1）的速率常数。在室温（298±4 K）下在18或25 Torr氩气中，得到的值分别为（k / 10 ^–13 cm ³分子^–1 s ^–1）= 1.53±0.15、0.55±0.1、10±2和9.5±2。我们的OH（v = 0）和OD（v = 0）的结果与其他工人的结果非常吻合。OH（v = 1）和OD（v认为1）与CO的反应对应于形成（HOCO）加合物的反应，该加合物可以分解为H + CO ₂或分解为OH + CO，但具有OH的振动弛豫。基于这个命题，已经对当OH，OD和CO碰撞时发生的基本过程进行了过渡态理论计算。计算成功地解释了这些系统中速率常数的值及其对温度，压力，同位素取代和试剂激发的依赖性。