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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reaction Dynamics of O(1D,3P) + OCS Studied with Time-Resolved Fourier Transform Infrared Spectroscopy and Quantum Chemical Calculations
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Reaction Dynamics of O(1D,3P) + OCS Studied with Time-Resolved Fourier Transform Infrared Spectroscopy and Quantum Chemical Calculations

机译：时间分辨傅立叶变换红外光谱法研究O（1D，3P）+ OCS的反应动力学和量子化学计算

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Time-resolved infrared emission of CO2 and OCS was observed in reactions O(3P) + OCS and O(1D) + OCS with a step-scan Fourier transform spectrometer. The CO2 emission involves Δν3 ) -1 transitions from highly vibrationally excited states, whereas emission of OCS is mainly from the transition (0, 0°, 1) f (0, 0°, 0); the latter derives its energy via near-resonant V-V energy transfer from highly excited CO2. Rotationally resolved emission lines of CO (V e 4 and J e 30) were also observed in the reaction O(1D) + OCS. For O(3P) + OCS, weak emission of CO2 diminishes when Ar is added, indicating that O(3P) is translationally hot to overcome the barrier for CO2 formation. The band contour of CO2 agrees with a band shape simulated on the basis of a Dunham expansion model of CO2; the average vibrational energy of CO2 in this channel is 49% of the available energy. This vibrational distribution fits with that estimated through a statistical partitioning of energy E* = 18 000 ( 500 cm-1 into all vibrational modes of CO2. For the reaction of O(1D) + OCS, approximately 51% of the available energy is converted into vibrational energy of CO2, and a statistical prediction using E* = 30 000 ( 500 cm-1 best fits the data. The mechanisms of these reactions are also investigated with the CCSD(T)/6-311+G(3df)//B3LYP/6-311+G(3df) method. The results indicate that the triplet O(3P) + OCS(X1Σ+) surface proceeds via direct abstraction and substitution channels with barriers of 27.6 and 36.4 kJ mol-1, respectively, to produce SO(X3Σ-) + CO(X1Σ+) and S(3P) + CO2(X1A1), whereas two intermediates, OSCO and SC(O)O, are formed from the singlet O(1D) + OCS(X1Σ+) surface without barrier, followed by decomposition to SO(a1Δ) + CO(X1Σ+) and S(1D) + CO2(X1A1), respectively. For the ground-state reaction O(3P) + OCS(X1Σ+), the singlet-triplet curve crossings play important roles in the observed kinetics and chemiluminescence.
机译：在O（3P）+ OCS和O（1D）+ OCS反应中，使用步进扫描傅立叶变换光谱仪观察到了时间分辨的CO2和OCS红外发射。 CO2的排放涉及从高振动激发态产生的Δν3-1转变，而OCS的排放主要来自（0，0°，1）f（0，0°，0）的转变;后者通过高激发CO2的近共振V-V能量转移获得能量。在O（1D）+ OCS反应中还观察到了旋转分解的CO发射线（V e 4和J e 30）。对于O（3P）+ OCS，添加Ar时，CO2的微弱排放会减少，这表明O（3P）在翻译上很热，可以克服CO2形成的障碍。二氧化碳的能带轮廓与基于二氧化碳的邓纳姆膨胀模型模拟的能带形状一致;在此通道中，CO2的平均振动能量为可用能量的49％。这种振动分布与通过统计能量E * = 18 000（500 cm-1进入CO2的所有振动模式）进行的统计估计相吻合。对于O（1D）+ OCS的反应，大约转化了51％的可用能量转化为CO2的振动能量，并使用E * = 30 000（500 cm-1最适合该数据进行统计预测。）还使用CCSD（T）/ 6-311 + G（3df）/研究了这些反应的机理/ B3LYP / 6-311 + G（3df）方法，结果表明三重态O（3P）+ OCS（X1Σ+）表面分别通过直接提取和取代通道进行，屏障分别为27.6和36.4 kJ mol-1，生成SO（X3Σ-）+ CO（X1Σ+）和S（3P）+ CO2（X1A1），而两个中间体OSCO和SC（O）O由单线态O（1D）+ OCS（X1Σ+ ）表面无障碍，然后分解为SO（a1Δ）+ CO（X1Σ+）和S（1D）+ CO2（X1A1）。对于基态反应O（3P）+ OCS（X1Σ+），单重态-三重态曲线交叉起着重要作用在观察到的动力学和化学发光中的作用。

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