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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Initial Mechanisms for the Decomposition of Electronically Excited Energetic Salts: TKX-50 and MAD-X1
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Initial Mechanisms for the Decomposition of Electronically Excited Energetic Salts: TKX-50 and MAD-X1

机译：电子激发高能盐分解的初始机制：TKX-50和MAD-X1

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摘要

Decomposition of energetic salts TKX-50 and MAD-X1 (dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate and dihydroxylammonium 3,3'-dinitro-5,5'-bis-1,2,4-triazole-1,1'-diol, respectively), following electronic state excitation, is investigated both experimentally and theoretically. The NO and N2 molecules are observed as initial decomposition products from the two materials subsequent to UV excitation. Observed NO products are rotationally cold (<25 K) and vibrationally hot (>1500 K). The vibrational temperature of the NO product from TKX-50 is (2600 +/- 250) K, (1100 +/- 250) K hotter than that produced from MAD-X1. Observed N-2 products of these two species are both rotationally cold (<30 K). Initial decomposition mechanisms for these two electronically excited salts are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(8,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanisms. Electronically excited S-1 molecules can nonadiabatically relax to the lower electronic state through (S-1/S-0)CI conical intersections. Both TKX-50 and MAD-X1 have two (S-1/S-0)CI conical intersections between S-1 and S-0 states, related to and leading to two different reaction paths, forming N-2 and NO products. N-2 products are released by the opening of the tetrazole or triazole rings of TKX-50 and MAD-X1. NO products are released from the amine N-oxide moiety of TKX-50, and for MAD-X1, they are produced through nitro-nitrite isomerizations. The observed rotational energy distributions for NO and N-2 products are consistent with the final structures of the respective transition states for each molecule on its S-0 potential energy surface.
机译：高能盐TKX-50和MAD-X1（5,5'-双四唑-1,1'-二醇盐和3,3'-二硝基-5,5'-双-1,2,4-三唑-在电子状态激发后，分别通过实验和理论研究了1,1'-二醇）。观察到NO和N2分子是紫外线激发后两种材料的初始分解产物。观察到的NO产品是旋转冷（<25 K）和振动热（> 1500 K）。 TKX-50的NO产物的振动温度比MAD-X1产生的温度高（2600 +/- 250）K，（1100 +/- 250）K。观察到的这两个物种的N-2产物都是旋转冷的（<30 K）。在完整的活动空间自洽场（CASSCF）级别上探索了这两种电子激发盐的初始分解机理。在CASSCF（8,8）/ 6-31G（d）级别的势能面计算表明，圆锥形相交在分解机制中起着至关重要的作用。电子激发的S-1分子可以通过（S-1 / S-0）CI圆锥形相交点绝热地松弛到较低的电子态。 TKX-50和MAD-X1都在S-1和S-0状态之间具有两个（S-1 / S-0）CI圆锥形交点，与两个不同的反应路径相关并导致两条不同的反应路径，从而形成N-2和NO产物。 N-2产物通过TKX-50和MAD-X1的四唑或三唑环打开而释放。没有产物从TKX-50的胺N-氧化物部分释放出来，对于MAD-X1，它们是通过亚硝酸盐异构化生成的。观察到的NO和N-2产物的旋转能分布与S-0势能表面上每个分子各自的过渡态的最终结构一致。

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