| 张宝森,张树海,苟瑞君,陈亚红,朱双飞,马坤.基于含时密度泛函理论的紫外光对太安的定性影响[J].装备环境工程,2022,19(12):48-53. ZHANG Bao-sen,ZHANG Shu-hai,GOU Rui-jun,CHEN Ya-hong,ZHU Shuang-fei,MA Kun.Qualitative Effects of Ultraviolet Light on PETN Based on TDDFT[J].Equipment Environmental Engineering,2022,19(12):48-53. |
| 基于含时密度泛函理论的紫外光对太安的定性影响 |
| Qualitative Effects of Ultraviolet Light on PETN Based on TDDFT |
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| DOI：10.7643/issn.1672-9242.2022.12.008 |
| 中文关键词: 太安 紫外光 含时密度泛函 吸收光谱 分子稳定性 激发态中图分类号:TJ450 文献标识码:A 文章编号:1672-9242(2022)12-0048-06 |
| 英文关键词:PETN ultraviolet TDDFT absorption spectrum molecular stability excited state |
| 基金项目:陕西应用物理化学研究所应用物理化学重点实验室基金(6142602200304) |
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| Author | Institution |
| ZHANG Bao-sen | School of Environmental and Safety Engineering, North University of China, Taiyuan, 030051, China |
| ZHANG Shu-hai | School of Environmental and Safety Engineering, North University of China, Taiyuan, 030051, China |
| GOU Rui-jun | School of Environmental and Safety Engineering, North University of China, Taiyuan, 030051, China |
| CHEN Ya-hong | School of Environmental and Safety Engineering, North University of China, Taiyuan, 030051, China |
| ZHU Shuang-fei | School of Environmental and Safety Engineering, North University of China, Taiyuan, 030051, China |
| MA Kun | Shaanxi Applied Physics-chemistry Research Institute, Xi'an 710061, China |
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| 中文摘要: |
| 目的 研究太安炸药在紫外光作用下的稳定性退化机制。方法 基于TDDFT(含时密度泛函)理论，在pbe1pbe/6-311G**水平下对太安分子50个激发态进行计算，依据计算结果，绘制吸收光谱，使用空穴–电子方法对最大吸收峰3个激发态(S9、S10和S11)的激发特征进行分析，这3个激发态对最大吸收峰的总贡献率达97.31%。将此3个激发态定为研究对象，对太安分子被特定的紫外光激发至激发态后弱键的Mayer和Laplace键级进行分析，并基于IFCT(Interfragment Charge Transfer)方法对太安分子激发至激发态过程中的电子转移情况进行描述。结果 太安紫外吸收光谱的最大吸收峰位置为186.6 nm，小于实验测试的吸收峰位置8.4 nm。对此吸收峰的强度贡献最大的3个激发态中，S9态贡献最高，为48.27%，其余2个激发态S10、S11为简并态，贡献相同，为24.52%。通过空穴–电子的电荷转移分析结果可知，3个激发态均存在整体激发并带有局域电荷转移的特征。PETN分子在吸收特定波长(187.00、186.92 nm)紫外光并激发至激发态时，O—NO2键的Mayer与Laplace键级均有所降低。结论 通过IFCT分析可知，引发键键级变化由O—NO2上的n→Pi*跃迁主导，这种效应会促使太安分子的稳定性降低。 |
| 英文摘要: |
| The work aims to study the stability degradation mechanism of PETN explosives under the action of ultraviolet light. Based on the TDDFT (time-dependent density functional) theory, 50 excited states of PETN molecules at the pbe1pbe/6-311G level were calculated and the ultraviolet absorption spectrum was drawn according to the calculation results, and the excitation characteristics of the three excited states of the maximum absorption peak (the total contribution rate of the three excited states of S9, S10, and S11 to the maximum absorption peak was 97.31%) were analyzed by the hole-electron method. These three excited states were set as the research objects to study the Mayer and Laplace bond orders of PETN molecules' weak bond after absorbing specific ultraviolet light. Finally, the electron transfer of PETN molecules excited to the excited states were described based on the IFCT (Interfragment Charge Transfer) method. The maximum absorption peak position of the PETN ultraviolet absorption spectrum calculated in this work was 186.6 nm, which was less than 8.4 nm of the absorption peak measured in experiment. Among the three excited states that contributed the most to this absorption peak, the S9 state had the highest contribution of 48.27%, and the other two excited states S10 and S11 were degenerate states with the same contribution of 24.52%. According to the results of the hole-electron analysis, all the three excited states had the characteristics of overall excitation and partial charge transfer. When the PETN molecules absorbed ultraviolet light of a specific wavelength (187.00 nm and 186.92 nm) and then was excited to the corresponding excited state, the Mayer and Laplace bond orders at O—NO2 bonds decreased. The IFCT analysis shows that the change of Mayer bond order is guided by the change from n→Pi on O—NO2. This effect may reduce the stability of PETN molecules. |
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