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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Experimental Rate Measurements for NS + NO, O_2 and NO_2, and Electronic Structure Calculations of the Reaction Paths for NS + NO_2
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Experimental Rate Measurements for NS + NO, O_2 and NO_2, and Electronic Structure Calculations of the Reaction Paths for NS + NO_2

机译：NS + NO，O_2和NO_2的实验速率测量以及NS + NO_2的反应路径的电子结构计算

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This study reports the first direct kinetic measurements on the NS radical. NS was produced by photolysis of N_4S_4 at 248 nm and was detected via laser-induced fluorescence. A fast reaction was observed between NS and NO_2, with k = (2.54 ± 0.12) * 10~(-11) cm~3 molecules~(-1) s~(-1) (error = 2σ including systematic errors) at 295 K. The rate coefficient shows a small negative temperature dependence over the range 295-673 K, which is represented by k = (2.57 ± 0.11) * 10~(-11)(T/295 K)~(-1.10±0.10) cm~3 molecule~(-1)s~(-1). The reaction was also investigated using density functional theory (B3LYP/6-31G**) to calculate the geometries of the stationary points on the potential energy surface, coupled with Brueckner doubles and perturbative triples to determine energy differences. The calculations show a direct route from reactants to N_2 + SO_2, via a series of isomers of NSNO_2, with no energy barrier higher than that of the entrance channel. It is also possible that the reaction forms SNO + NO; this channel has a higher barrier than that found on the N_2 + SO_2 route, which is also below the entrance channel, but involves fewer isomerizations. No reaction was observed between NS and O_2 or NO, at temperatures up to 623 K and upper limits of 1 * 10~(-15) and 3 * 10~(-14) cm~3 molecule~(-1) s~(-1), respectively, were placed on these rate coefficients.
机译：这项研究报告了对NS自由基的首次直接动力学测量。 NS是通过N_4S_4在248 nm处的光解产生的，并通过激光诱导的荧光进行检测。在NS和NO_2之间观察到快速反应，k =（2.54±0.12）* 10〜（-11）cm〜3分子〜（-1）s〜（-1）（误差=2σ，包括系统误差）在295 K.速率系数在295-673 K范围内显示出较小的负温度依赖性，其表示为k =（2.57±0.11）* 10〜（-11）（T / 295 K）〜（-1.10±0.10） cm〜3分子〜（-1）s〜（-1）。还使用密度泛函理论（B3LYP / 6-31G **）对反应进行了研究，以计算势能表面上固定点的几何形状，并与Brueckner倍增和扰动三倍结合确定能量差。计算结果表明，通过一系列NSNO_2异构体，从反应物到N_2 + SO_2的直接路线没有比入口通道高的能垒。反应也有可能形成SNO + NO;该通道具有比N_2 + SO_2路线更高的势垒，后者也位于入口通道下方，但异构化较少。在高达623 K的温度和上限1 * 10〜（-15）和3 * 10〜（-14）cm〜3分子〜（-1）s〜（ -1）分别放在这些速率系数上。

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