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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Evaluation of data for atmospheric models: Master equation/RRKM calculations on the combination reaction, BrO+NO2 - BrONO2, a conundrum
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Evaluation of data for atmospheric models: Master equation/RRKM calculations on the combination reaction, BrO+NO2 - BrONO2, a conundrum

机译：大气模型数据的评估：结合反应的主方程/ RRKM计算，BrO + NO2-> BrONO2，一个难题

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Experimental data for the title reaction were modeled using master equation (ME)/RRKM methods based on the Multiwell suite of programs. The starting point for the exercise was the empirical fitting provided by the NASA (Sander, S. P.; Finlayson-Pitts, B. J.; Friedl, R. R.; Golden, D. M.; Huie, R. E.; Kolb, C. E.; Kurylo, M. J.; Molina, M. J.; Moortgat, G. K.; Orkin, V. L.; Ravishankara, A. R. Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15; Jet Propulsion Laboratory: Pasadena, California, 2006)(1) and IUPAC (Atkinson, R.; Baulch, D. L.; Cox, R. A.: R. F. Hampson, J.; Kerr, J. A.; Rossi, M. J.; Troe, J. J. Phys. Chem. Ref. Data. 2000, 29, 167) 2 data evaluation panels, which represents the data in the experimental pressure ranges rather well. Despite the availability of quite reliable parameters for these calculations (molecular vibrational frequencies (Parthiban, S.; Lee, T. J. J. Chem. Phys. 2000, 113, 145)3 and a. value (Orlando, J. J.; Tyndall, G. S. J. Phys. Chem. 1996, 100,. 19398)4 of the bond dissociation energy, D-298(BrO-NO2) = 118 kJ mol(-1), corresponding to Delta H-0(circle) = 114.3 kJ mol(-1) at 0 K) and the use of RRKM/ME methods, fitting calculations to the reported data or the empirical equations was anything but straightforward. Using these molecular parameters resulted in a discrepancy between the calculations and the database of rate constants of a factor of ca. 4 at, or close to, the low-pressure limit. Agreement between calculation and experiment could be achieved in two ways, either by increasing Delta H-0(circle) to an unrealistically high value (149.3 kJ mol(-1)) or by increasing , the average energy transferred in a downward collision, to an unusually large value (> 5000 cm(-1)). The discrepancy could also be reduced by making all overall rotations fully active. The system was relatively insensitive to changing the moments of inertia in the transition state to increase the centrifugal effect. The possibility of involvement of BrOONO was tested and cannot account for the difficulties of fitting the data.
机译：基于Multiwell程序套件，使用主方程（ME）/ RRKM方法对标题反应的实验数据进行建模。这项练习的起点是由美国国家航空航天局提供的经验拟合（SP，Sander; BJ Finlayson-Pitts; RR，Friedl; DM，Golden; DM; Huie，CE; CE; Kurylo; MJ; Molina，MJ; Moortgat） ，GK; Orkin，VL; Ravishankara，AR用于大气研究的化学动力学和光化学数据，评估编号15;喷气推进实验室：加利福尼亚州帕萨迪纳，2006年）（1）和IUPAC（Atkinson，R。; Baulch，DL）; Cox，RA：RF Hampson，J .; Kerr，JA; Rossi，MJ; Troe，JJ Phys。Chem。Ref。Data。2000，29，167）2个数据评估板，分别代表了实验压力范围内的数据好。尽管有相当可靠的参数可用于这些计算（分子振动频率（Parthiban，S .; Lee，TJJ Chem。Phys。2000，113，145））3和a。值（Orlando，JJ; Tyndall，GSJ Phys。Chem。 1996，100 ,. 19398）4的键解离能D-298（BrO-NO2）= 118 kJ mol（-1），对应于0时的Delta H-0（圆）= 114.3 kJ mol（-1） K）以及使用RRKM / ME方法，将计算与报告数据或经验方程式拟合的过程非常简单。使用这些分子参数会导致计算结果与速率常数数据库的差异约为ca。 4处于或接近低压极限。计算和实验之间的一致性可以通过两种方式达成，一种是将Delta H-0（圆圈）增加到一个不切实际的高值（149.3 kJ mol（-1）），另一种是通过增加，即向下碰撞，达到异常大的值（> 5000 cm（-1））。也可以通过使所有整体旋转完全有效来减少差异。该系统对改变过渡状态下的惯性矩以增加离心效果相对不敏感。已测试了BrOONO参与的可能性，无法说明拟合数据的困难。

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