碘分子在COIL体系中的碰撞解离动力学研究

With the development of chemical oxygen-iodine laser (COIL) recently, requirements of the output energy, the beam quality and the energy efficiency are rapidly increased. To resolve the bottleneck of the low conversion of energy v.s. mass and volume, engineers have to obtain more detailed information of the inside chemical reaction mechanism in COIL. Therefore, this project is aimed to explore the mechanism of I2(X) collisional dissociation. Based on our patented coherent anti-Stokes Raman spectrum (CARS) apparatus and the quantum chemistry calculation, I2(X) dissociation mechanism is investigated. Firstly, it will be detected whether the I2(A′) and I2(A) states participate in I2(X) dissociation process or not. Secondly, the impact of reactants fluent on CARS signal intensity of I2(A′) and I2(A) will be also concluded. Finally, the most effective route for I2(X) dissociation will be discussed under COIL working condition. Through this project, it is expected to identify the importance of I2(A′) and I2(A) states in the I2 collision dissociation process in COIL, to get clearer mechanism for the I2(X) dissociation, and also to provide fundamental theoretical support for establishing higher energy efficiency COIL unit.

随着氧碘化学激光（COIL）研究的不断深入，其激光能量指标、光束质量指标和能量效率指标等要求越来越高，特别是面对质量高效化难题，人们不得不再次关注COIL更为详细的反应机理。因此，为了进一步探索I2(X)碰撞解离机理，本项目将以自行搭建的相干反斯托克斯拉曼光谱仪（CARS）为主，结合量子化学理论计算方法，研究基态碘分子在COIL体系中的碰撞解离动力学，首先探测I2(A′)和I2(A)两个电子态是否参与解离过程；然后进一步考察各个反应物流量对CARS探测I2(A′)和/或I2(A)中间态信号强度的影响，从而解析特定工况下I2(X)最优解离通道。通过该项目的实施，希望最终确认I2(A′)和I2(A)两个电子态在I2(X)在COIL体系中的碰撞解离动力学过程中的参与程度，进一步明晰I2(X)碰撞解离机理；更希望为当前能量高效化COIL研制任务在结构参数设计上提供基础性的理论支持。

本项目的研究是按照计划正常进行。在执行过程中，由于碘分子/碘原子太重，外层电子轨道众多，利用MOLPRO 量化计算软件包计算碘分子的最低5个电子态势能曲线（含基态），没有获得足够的收敛数据，也就没有将其势能曲线精度提高到约15 cm-1 量级（即0.05 kcal/mol）。与此同时，我们对模型进行进一步简化，采用改进型的经典轨线方法，偶然发现对COH+H等体系有很好的收敛效果，进而对上述反应做了一系列的研究，发现了一些其他的现象，取得了一些研究成果，以论文形式（5篇，全部为SCI收录）发表在国际期刊上。