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The exploration of Mars has attracted increasing interest in these years. The experiments and simulations show that strong electric field triggered by the dust storms in the Martian atmosphere may cause CO2 discharge. Studies on this phenomenon will not only help deepen our comprehension on the evolution of Martian surface, but also provide a possibility to realize the in-situ oxygen generation on Mars based on plasma chemistry. In this paper, a zero-dimensional global model is used to simplify the complicated description of CO2 chemical kinetics, therefore a reduced chemistry can be obtained for detailed numerical simulation in the near future. At the beginning of simplification, the graph theoretical analysis is used to pre-treat the original model by exploring the relationship between reacting species. Through the study of connectivity and the topological network, species such as O2, e, and CO prove to be important in the information transmission of the network. While gaining a clearer understanding of the chemistry model, dependence analysis will be used to investigate numerical simulation results. In this way a directed relation diagram can be obtained, where the influence between different species is quantitively explained in terms of numerical solutions. Users could keep different types of species correspondingly according to their own needs, and in this paper, some species with low activeness such as C2O,
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图 1 地球大气环境下CO2放电转化率对比
Figure 1. Comparations of CO2 discharge conversion in the earth atmosphere.
图 2 各粒子所参与的反应数目
Figure 2. Number of reactions that each species participates in
图 3 可通过反应直接建立联系的粒子种类数目
Figure 3. Number of species that can be directly connected by reactions.
图 4 各粒子度数 (a)出度、入度的条形堆积图; (b)粒子在出度-入度空间的分布情况
Figure 4. Degrees of species: (a) Stacked bars of in-degree and out-degrees; (b) distribution of species in the out-degree-in-degree space.
图 5 粒子网络拓扑图
Figure 5. Species network topology.
图 6 粒子在临近-相间中心性空间的分布图
Figure 6. Distribution of species in the closeness-betweenness centrality space.
图 7 粒子在集聚系数-度数空间的分布
Figure 7. Distribution of species in the clustering coefficient-degree space.
图 8 基于CO2的各中性粒子间的相互关系有向图
Figure 8. Directed relation graph among neutral species based on CO2.
图 9 基于e的各带电粒子间的相互关系有向图
Figure 9. Directed relation graph among charged species based on electrons.
图 10 初始集合所有粒子间相互关系有向图
Figure 10. Directed relation graph of the original model among all species.
图 11
$ {\mathrm{C}\mathrm{O}}_{2}^{+} $ 在所参与的各项反应中的反应速率Figure 11. Reaction rates of
$ {\mathrm{C}\mathrm{O}}_{2}^{+} $ in each reaction involved.
图 12 初始集合中由碰撞截面描述的电子碰撞电离反应的比重
Figure 12. Proportion of electron impact ionization reactions described by collision cross sections in the original model.
图 13 初始集合(实线)与简化集(虚线)关于粒子浓度的数值模拟结果比较 (a)中性粒子; (b)正离子; (c)电子与负离子
Figure 13. Comparison of the numerical simulation results of particle concentration between the original model (solid line) and the simplified model (dashed line): (a) Neutrals; (b) positive ions; (c) electron and negative ions.
图 14 3 ms时引起(a) CO和(b) O2浓度变化的主要反应
Figure 14. Main reactions at 3 ms which cause density changes of (a) CO and (b) O2.
图 15 作为比能量输入的函数, 简化集合与初始集合关于转化率与能量方面的比较 (a) CO2转化率; (b)能量效率; (c)能量损耗
Figure 15. As a function of SEI, comparations of original and simplified model on (a) conversion of CO2, (b) energy efficiency, (c) energy cost.
表 A1 初始反应集合中的粒子构成
Table A1. Composition of particles in the original model.
初始集合粒子构成 中性粒子 CO2, CO, C, O, O2, O3, C2O 正离子 $ {\mathrm{C}\mathrm{O}}_{4}^{+} $, $ {\mathrm{C}\mathrm{O}}_{2}^{+} $, CO+, C+, O+, $ {\mathrm{O}}_{2}^{+} $, $ {\mathrm{O}}_{4}^{+} $,
$ {\mathrm{O}}_{5}^{+} $, $ {\mathrm{C}}_{2}{\mathrm{O}}_{2}^{+} $, $ {\mathrm{C}}_{2}{\mathrm{O}}_{3}^{+} $, $ {\mathrm{C}}_{2}{\mathrm{O}}_{4}^{+} $负离子 $ {\mathrm{C}\mathrm{O}}_{4}^{-} $, $ {\mathrm{C}\mathrm{O}}_{3}^{-} $, O–, $ {\mathrm{O}}_{2}^{-} $, $ {\mathrm{O}}_{3}^{-} $, $ {\mathrm{O}}_{4}^{-} $ 
DownLoad: CSV
表 A2 初始集合中由碰撞截面描述的电子碰撞反应
Table A2. Electron impact reactions described by collision cross sections in the original model.
序号 反应 文献 (X01) e + CO2 $ \Rightarrow $ $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + 2e [50] (X02) e + CO2 $ \Rightarrow $ CO + O + e [50] (X03) e + CO2 $ \Rightarrow $ CO + O– [50] (X04) e + CO2 $ \Rightarrow $ 2e + O + CO+ [50] (X05) e + CO2 $ \Rightarrow $ 2e + CO + O+ [50] (X06) e + CO2 $ \Rightarrow $ 2e + C+ + O2 [50] (X07) e + CO2 $ \Rightarrow $ $ {\mathrm{O}}_{2}^{+} $ + C + 2e [51, 52] (X08) e + CO $ \Rightarrow $ C + O– [50] (X09) e + CO $ \Rightarrow $ e + C + O [50] (X10) e + CO $ \Rightarrow $ 2e + CO+ [50] (X11) e + CO $ \Rightarrow $ 2e + C + O+ [50] (X12) e + CO $ \Rightarrow $ 2e + C+ + O [50] (X13) e + O3 $ \Rightarrow $ $ {{\mathrm{O}}_{2}^{-}}^{-} $ + O [50] (X14) e + O3 $ \Rightarrow $ O2 + O– [50] (X15) e + O3 $ \Rightarrow $ O + O2 + e [53] (X16) e + O3 $ \Rightarrow $ $ {\mathrm{O}}_{2}^{+} $ + O + 2e [53] (X17) e + O3 $ \Rightarrow $ O+ + O– + O + e [53] (X18) e + O2 $ \Rightarrow $ 2 O + e [50] (X19) e + O2 $ \Rightarrow $ O + O– [50] (X20) e + O2 $ \Rightarrow $ 2e + $ {\mathrm{O}}_{2}^{+} $ [50] (X21) e + O2 $ \Rightarrow $ 2e + O + O+ [50] (X22) e + O2 $ \Rightarrow $ e + O+ + O– [50, 54] (X23) e + O $ \Rightarrow $ 2e + O+ [50] (X24) e + C $ \Rightarrow $ 2e + C+ [50]
DownLoad: CSV
表 A5 初始集合中的离子-中性和离子-离子反应, 其中Tg为气体温度, 单位是K, 速率系数的单位在二体或三体反应中分别是m3/s或m6/s
Table A5. Ion-neutral and ion-ion reactions in the original model. Tg is the gas temperature in K. The rate coefficients are in m3/s or m6/s for binary or ternary reactions.
序号 反应 反应速率系数 文献 (I01) O– + CO2 $ \Rightarrow$ O + CO2 + e 4.0 × 10–18 [48] (I02) O– + CO2 + CO $ \Rightarrow$ $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + CO 1.5 × 10–40 [61] (I03) O– + CO2 + O2 $ \Rightarrow$ $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + O2 3.1 × 10–40 [61] (I04) O– + CO2 + CO2 $ \Rightarrow$ $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + CO2 9.0 × 10–41 [52] (I05) $ {\mathrm{O}}_{2}^{-} $ + CO2 + O2 $ \Rightarrow$ $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ + O2 4.7 × 10–41 [52] (I06) $ {\mathrm{O}}_{3}^{-} $+ CO2 $ \Rightarrow$ $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + O2 5.5 × 10–16 [18] (I07) $ {\mathrm{O}}_{4}^{-} $ + CO2 $ \Rightarrow$ O2 + $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ 4.8 × 10–16 [18] (I08) O+ + CO2 $ \Rightarrow$ $ {\mathrm{O}}_{2}^{+} $ + CO 9.4 × 10–16 [18] (I09) O+ + CO2 $ \Rightarrow$ O + $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ 4.5 × 10–16 [18] (I10) C+ + CO2 $ \Rightarrow$ CO+ + CO 1.1 × 10–15 [18] (I11) $ {\mathrm{O}}_{2}^{+} $ + CO2 + M $ \Rightarrow$ $ {\mathrm{C}\mathrm{O}}_{4}^{+} $ + M 2.3 × 10–41 [18] (I12) $ {\mathrm{O}}_{5}^{+} $ + CO2 $ \Rightarrow$ $ {\mathrm{C}\mathrm{O}}_{4}^{+} $ + O3 1.0 × 10–17 [52] (I13) CO+ + CO2 $ \Rightarrow$ $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + CO 1.0 × 10–15 [56] (I14) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + CO2 + M $ \Rightarrow$ $ {\mathrm{C}}_{2}{\mathrm{O}}_{4}^{+} $ + M 3.0 × 10–40 [18] (I15) O+ + CO $ \Rightarrow$ O + CO+ 4.9 × 10–18(Tg/298)0.5exp(–4580/Tg) [18] (I16) C+ + CO $ \Rightarrow$ CO+ + C 5.0 × 10–19 [18] (I17) $ {\mathrm{C}}_{2}{\mathrm{O}}_{3}^{+} $ + CO $ \Rightarrow$ CO2 + $ {\mathrm{C}}_{2}{\mathrm{O}}_{2}^{+} $ 1.1 × 10–15 [18] (I18) $ {\mathrm{C}}_{2}{\mathrm{O}}_{4}^{+} $ + CO $ \Rightarrow$ CO2 + $ {\mathrm{C}}_{2}{\mathrm{O}}_{3}^{+} $ 9.0 × 10–16 [18] (I19) $ {\mathrm{C}}_{2}{\mathrm{O}}_{3}^{+} $ + CO + M $ \Rightarrow$ CO2 + $ {\mathrm{C}}_{2}{\mathrm{O}}_{2}^{+} $ + M 2.6 × 10–38 [18] (I20) $ {\mathrm{C}}_{2}{\mathrm{O}}_{4}^{+} $ + CO + M $ \Rightarrow$ CO2 + $ {\mathrm{C}}_{2}{\mathrm{O}}_{3}^{+} $ + M 4.2 × 10–38 [18] (I21) O– + CO $ \Rightarrow$ CO2 + e 5.5 × 10–16 [44] (I22) $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + CO $ \Rightarrow$ 2CO2 + e 5.0 × 10–19 [58] (I23) $ {\mathrm{O}}_{2}^{+} $ + C $ \Rightarrow$ CO+ + O 5.2 × 10–17 [18] (I24) $ {\mathrm{O}}_{2}^{+} $ + C $ \Rightarrow$ C+ + O2 5.2 × 10–17 [18] (I25) CO+ + C $ \Rightarrow$ CO + C+ 1.1 × 10–16 [18] (I26) O– + C $ \Rightarrow$ CO + e 5.0 × 10–16 [57] (I27) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + O $ \Rightarrow$ $ {\mathrm{O}}_{2}^{+} $ + CO 1.638 × 10–16 [52] (I28) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + O $ \Rightarrow$ CO2 + O+ 9.62 × 10–17 [18] (I29) CO+ + O $ \Rightarrow$ CO + O+ 1.4 × 10–16 [18] (I30) $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ + O $ \Rightarrow$ $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + O2 1.1 × 10–16 [18] (I31) $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ + O $ \Rightarrow$ CO2 + O2 + O– 1.4 × 10–17 [18] (I32) $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ + O $ \Rightarrow$ CO2 + $ {\mathrm{O}}_{3}^{-} $ 1.4 × 10–16 [18] (I33) $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + O $ \Rightarrow$ CO2 + $ {\mathrm{O}}_{2}^{-} $ 8.0 × 10–17 [58] (I34) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + O2 $ \Rightarrow$ $ {\mathrm{O}}_{2}^{+} $ + CO2 6.4 × 10–17 [52] (I35) CO+ + O2 $ \Rightarrow$ $ {\mathrm{O}}_{2}^{+} $ + CO 1.2 × 10–16 [18] (I36) C+ + O2 $ \Rightarrow$ CO + O+ 6.2 × 10–16 [18] (I37) C+ + O2 $ \Rightarrow$ CO+ + O 3.8 × 10–16 [18] (I38) $ {\mathrm{C}}_{2}{\mathrm{O}}_{2}^{+} $ + O2 $ \Rightarrow$ 2CO + $ {\mathrm{O}}_{2}^{+} $ 5.0 × 10–18 [18] (I39) $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ + O3 $ \Rightarrow$ CO2 + $ {\mathrm{O}}_{3}^{-} $ + O2 1.3 × 10–16 [18] (I40) $ {\mathrm{C}\mathrm{O}}_{4}^{+} $ + O3 $ \Rightarrow$ $ {\mathrm{O}}_{5}^{+} $ + CO2 1.0 × 10–16 [52] (I41) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + O– $ \Rightarrow$ O + CO2 1.0 × 10–13 [62] (I42) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + $ {\mathrm{O}}_{2}^{-} $ $ \Rightarrow$ CO + O2 + O 6.0 × 10–13 [44] (I43) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ $ \Rightarrow$ 2CO2 + O 5.0 × 10–13 [58] (I44) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ $ \Rightarrow$ 2CO2 + O2 5.0 × 10–13 [18] (I45) CO+ + $ {\mathrm{O}}_{2}^{-} $ $ \Rightarrow$ CO + O2 2.0 × 10–13 [55] (I46) C+ + O– $ \Rightarrow$ C + O 5.0 × 10–14 [55] (I47) C+ + $ {\mathrm{O}}_{2}^{-} $ $ \Rightarrow$ C + O2 5.0 × 10–14 [55] (I48) O–+ CO+ $ \Rightarrow$ CO + O 1.0 × 10–13 [62] (I49) $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow$ CO2 + O2 + O 3.0 × 10–13 [18] (I50) $ {\mathrm{O}}_{2}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ $ \Rightarrow$ CO2 + 2O2 3.0 × 10–13 [18] (I51) $ {\mathrm{C}}_{2}{\mathrm{O}}_{2}^{+} $ + M $ \Rightarrow$ CO+ + CO + M 1.0 × 10–18 [18] (I52) $ {\mathrm{C}}_{2}{\mathrm{O}}_{2}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{3}^{-} $$ \Rightarrow$ CO2 + 2CO + O 5.0 × 10–13 [18] (I53) $ {\mathrm{C}}_{2}{\mathrm{O}}_{2}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ $ \Rightarrow$ CO2 + 2CO + O2 5.0 × 10–13 [18] (I54) $ {\mathrm{C}}_{2}{\mathrm{O}}_{2}^{+} $ + $ {\mathrm{O}}_{2}^{-} $$ \Rightarrow$ 2CO + O2 6.0 × 10–13 [18] (I55) $ {\mathrm{C}}_{2}{\mathrm{O}}_{3}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ $ \Rightarrow$ 2CO2 + CO + O 5.0 × 10–13 [18] (I56) $ {\mathrm{C}}_{2}{\mathrm{O}}_{3}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ $ \Rightarrow$ 2CO2 + CO + O2 5.0 × 10–13 [18] (I57) $ {\mathrm{C}}_{2}{\mathrm{O}}_{3}^{+} $ + $ {\mathrm{O}}_{2}^{-} $ $ \Rightarrow$ CO2 + CO + O2 6.0 × 10–13 [18] (I58) $ {\mathrm{C}}_{2}{\mathrm{O}}_{4}^{+} $ + M $ \Rightarrow$ $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + CO2 + M 1.0 × 10–20 [18] (I59) $ {\mathrm{C}}_{2}{\mathrm{O}}_{4}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{3}^{-} $$ \Rightarrow$ 3CO2 + O 5.0 × 10–13 [18] (I60) $ {\mathrm{C}}_{2}{\mathrm{O}}_{4}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ $ \Rightarrow$ 3CO2 + O2 5.0 × 10–13 [18] (I61) $ {\mathrm{C}}_{2}{\mathrm{O}}_{4}^{+} $ + $ {\mathrm{O}}_{2}^{-} $ $ \Rightarrow$ 2CO2 + O2 6.0 × 10–13 [18] (I62) O–+ O3 $ \Rightarrow$ 2O2 + e 3.0 × 10–16 [44] (I63) O–+ O3 $ \Rightarrow$ $ {\mathrm{O}}_{3}^{-} $ + O 8.0 × 10–16 [18] (I64) $ {\mathrm{O}}_{2}^{-} $ + O3 $ \Rightarrow$ $ {\mathrm{O}}_{3}^{-} $ + O2 4.0 × 10–16 [18] (I65) $ {\mathrm{O}}_{3}^{-} $ + O3 $ \Rightarrow$ 3O2 + e 3.0 × 10–16 [18] (I66) O+ + O3 $ \Rightarrow$ $ {\mathrm{O}}_{2}^{+} $ + O2 1.0 × 10–16 [18] (I67) O– + O2 $ \Rightarrow$ O3 + e 1.0 × 10–18 [44] (I68) O– + O2 $ \Rightarrow$ $ {\mathrm{O}}_{2}^{-} $ + O 1.5 × 10–18 [55] (I69) O– + O2 $ \Rightarrow$ O + e + O2 6.9 × 10–16 [52] (I70) O– + O2 + O2 $ \Rightarrow$ $ {\mathrm{O}}_{3}^{-} $ + O2 1.1 × 10–42(Tg/300) [52] (I71) $ {\mathrm{O}}_{2}^{-} $ + O2 $ \Rightarrow$ 2O2 + e 2.7 × 10–16(Tg/300)0.5exp(–5590/Tg) [52] (I72) $ {\mathrm{O}}_{2}^{-} $ + O2 + M $ \Rightarrow$ $ {\mathrm{O}}_{4}^{-} $ + M 3.5 × 10–43 [18] (I73) $ {\mathrm{O}}_{3}^{-} $ + O2 $ \Rightarrow$ O2 + O3 + e 2.3 × 10–17 [18] (I74) O+ + O2 $ \Rightarrow$ O + $ {\mathrm{O}}_{2}^{+} $ 1.9 × 10–17(Tg/298)–0.5 [18] (I75) $ {\mathrm{O}}_{2}^{+} $ + O2 + O2 $ \Rightarrow$ $ {\mathrm{O}}_{4}^{+} $ + O2 4.0 × 10–42(Tg/300)–2.93 [52] (I76) $ {\mathrm{O}}_{4}^{+} $ + O2 $ \Rightarrow$ $ {\mathrm{O}}_{2}^{+} $ + O2 + O2 1.8 × 10–19 [52] (I77) O+ + O + O2 $ \Rightarrow$ $ {\mathrm{O}}_{2}^{+} $ + O2 1.0 × 10–41 [52] (I78) O– + O $ \Rightarrow$ O2 + e 2.3 × 10–16 [21] (I79) $ {\mathrm{O}}_{2}^{-} $ + O $ \Rightarrow$ O2 + O– 3.31 × 10–16 [21] (I80) $ {\mathrm{O}}_{2}^{-} $ + O $ \Rightarrow$ O3 + e 3.3 × 10–16 [18] (I81) $ {\mathrm{O}}_{3}^{-} $ + O $ \Rightarrow$ O3 + O– 1.0 × 10–19 [18] (I82) $ {\mathrm{O}}_{3}^{-} $ + O $ \Rightarrow$ 2O2 + e 1.0 × 10–19 [18] (I83) $ {\mathrm{O}}_{3}^{-} $ + O $ \Rightarrow$ $ {\mathrm{O}}_{2}^{-} $ + O2 2.5 × 10–16 [18] (I84) $ {\mathrm{O}}_{4}^{-} $ + O $ \Rightarrow$ $ {\mathrm{O}}_{3}^{-} $ + O2 4.0 × 10–16 [18] (I85) $ {\mathrm{O}}_{4}^{-} $ + O $ \Rightarrow$ O– + 2O2 3.0 × 10–16 [18] (I86) $ {\mathrm{O}}_{4}^{+} $ + O $ \Rightarrow$ $ {\mathrm{O}}_{2}^{+} $ + O3 3.0 × 10–16 [18] (I87) O– + $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow$ O2 + O 2.6 × 10–14(300/Tg)0.44 [21] (I88) O– + $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow$ 3O 4.2 × 10–13(300/Tg)0.44 [21] (I89) O– + $ {\mathrm{O}}_{2}^{+} $ + O2 $ \Rightarrow$ O3 + O2 2.0 × 10–37 [57] (I90) O– + O+ + O $ \Rightarrow$ O2 + O 2.0 × 10–37 [57] (I91) O– + O+ + O2 $ \Rightarrow$ 2O2 2.0 × 10–37 [57] (I92) O– + O+ $ \Rightarrow$ 2O 4.0 × 10–14 [18] (I93) $ {\mathrm{O}}_{2}^{-} $ + O+ $ \Rightarrow$ O + O2 2.7 × 10–13 [18] (I94) $ {\mathrm{O}}_{2}^{-} $ + O+ + O2 $ \Rightarrow$ O3 + O2 2.0 × 10–37 [57] (I95) $ {\mathrm{O}}_{2}^{-} $ + $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow$ 2O2 2.01 × 10–13(300/Tg)0.5 [21] (I96) $ {\mathrm{O}}_{2}^{-} $ + $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow$ O2 + 2O 4.2 × 10–13 [21] (I97) $ {\mathrm{O}}_{2}^{-} $ + $ {\mathrm{O}}_{2}^{+} $ + O2 $ \Rightarrow$ 3O2 2.0 × 10–37 [57] (I98) $ {\mathrm{O}}_{3}^{-} $ + O + M $ \Rightarrow$ O3 + O + M 2.0 × 10–37(Tg/300)–2.5 [57] (I99) $ {\mathrm{O}}_{3}^{-} $ + $ {\mathrm{O}}_{2}^{+} $ + M $ \Rightarrow$ O3 + O2 + M 2.0 × 10–37(Tg/300)–2.5 [57] (I100) $ {\mathrm{O}}_{3}^{-} $ + O+ $ \Rightarrow$ O3 + O 1.0 × 10–13 [18] (I101) $ {\mathrm{O}}_{3}^{-} $+ $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow$ O2 + O3 2.0 × 10–13 [18] (I102) $ {\mathrm{O}}_{3}^{-} $ + $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow$ 2O + O3 1.0 × 10–13 [18] (I103) $ {\mathrm{O}}_{4}^{-} $ + M $ \Rightarrow$ $ {\mathrm{O}}_{2}^{-} $ + O2 + M 4.0 × 10–18 [18]
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表 B1 简化集合中的粒子构成
Table B1. Composition of particles in the simplified model.
简化集合粒子构成 中性粒子 CO2, CO, C, O, O2, O3 正离子 $ {\mathrm{C}\mathrm{O}}_{2}^{+} $, CO+, C+, O+, $ {\mathrm{O}}_{2}^{+} $ 负离子 $ {\mathrm{C}\mathrm{O}}_{4}^{-} $, $ {\mathrm{C}\mathrm{O}}_{3}^{-} $, O–, $ {\mathrm{O}}_{2}^{-} $, $ {\mathrm{O}}_{3}^{-} $
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表 A3 初始集合中由反应速率系数描述的电子碰撞反应, 其中Te为电子温度, 单位是eV; Tg为气体温度, 单位是K; 速率系数的单位在二体或三体反应中分别是m3/s或m6/s
Table A3. Electron impact reactions described by rate coefficients in the original model. Te is the electron temperature in eV and Tg is the gas temperature in K. The rate coefficients are in m3/s or m6/s for binary or ternary reactions.
序号 反应 反应速率系数 文献 (E01) e + e + C+ $\Rightarrow $ C + e 5.0 × 10–39 [55] (E02) e + CO+ $\Rightarrow $ C + O 3.46 × 10–14Te–0.48 [56] (E03) e + $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ $\Rightarrow $ C + O2 3.94 × 10–13Te–0.4 [21] (E04) e + $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ $\Rightarrow $ CO + O 2.0 × 10–11Te–0.5Tg–1 [18] (E05) e + $ {\mathrm{C}\mathrm{O}}_{4}^{+} $ $\Rightarrow $ CO2 + O2 1.61 × 10–13Te–0.5 [18] (E06) e + $ {\mathrm{C}}_{2}{\mathrm{O}}_{2}^{+} $ $\Rightarrow $ 2CO 4.0 × 10–13Te–0.34 [18] (E07) e + $ {\mathrm{C}}_{2}{\mathrm{O}}_{3}^{+} $ $\Rightarrow $ CO2 + CO 5.4 × 10–14Te–0.7 [18] (E08) e + $ {\mathrm{C}}_{2}{\mathrm{O}}_{4}^{+} $ $\Rightarrow $ 2CO2 2.0 × 10–11Te–0.5Tg–1 [18] (E09) e + O2 + O2 $\Rightarrow $ $ {\mathrm{O}}_{2}^{-} $ + O2 2.2 × 10–41(300/Tg)1.5exp(-600/Tg) [52] (E10) e + O + O2 $\Rightarrow $ O– + O2 1.0 × 10–43exp(300/Tg) [52] (E11) e + O3 + O2 $\Rightarrow $ $ {\mathrm{O}}_{3}^{-} $ + O2 4.6 × 10–40 [52] (E12) e + O+ + M $\Rightarrow $ O + M 6.0 × 10–39(Te × 38.67)–1.5 [57] (E13) e + $ {\mathrm{O}}_{2}^{+} $ $\Rightarrow $ 2O 6.0 × 10–13Te–0.5(1/Tg)0.5 [21] (E14) e + $ {\mathrm{O}}_{2}^{+} $ + M $\Rightarrow $ O2 + M 6.0 × 10–39(Te × 38.67)–1.5 [57] (E15) e + $ {\mathrm{O}}_{2}^{+} $ + e $\Rightarrow $ O2 + e 1.0 × 10–31(Te × 38.67)–4.5 [57] (E16) e + O+ + e $\Rightarrow $ O + e 7.2 × 10–32(Te × 38.67)–4.5 [57] (E17) e + $ {\mathrm{O}}_{4}^{+} $ $\Rightarrow $ 2O2 2.25 × 10–13Te–0.5 [18] (E18) e + $ {\mathrm{O}}_{5}^{+} $ $\Rightarrow $ O2 + O3 5.0 × 10–12(Te × 38.67)–0.6 [52]
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表 A4 初始集合中的中性粒子反应, 其中 Tg 为气体温度, 单位是 K; 速率系数的单位在二体或三体反应中分别是 m3/s 或 m6/s
Table A4. Reaction of neutrals in the original model. Tg is the gas temperature in K. The rate coefficients are in m3/s or m6/s for binary or ternary reactions.
序号 反应 反应速率系数 文献 (N01) CO2 + O $ \Rightarrow$ CO + O2 2.8 × 10–17exp(–26500/Tg) [21] (N02) CO + O2 $ \Rightarrow$ CO2 + O 4.2 × 10–18exp(–24000/Tg) [21] (N03) CO2 + C $ \Rightarrow$ 2CO 1.0 × 10–21 [21] (N04) C + O2 $ \Rightarrow$ O + CO 3.0 × 10–17 [21] (N05) C + O + M $ \Rightarrow$ M + CO 2.14 × 10–41(Tg/300)–3.08exp(–2114/Tg) [21] (N06) CO + M $ \Rightarrow$ O + C + M 1.52 × 10–10(Tg/298)–3.1exp(–129000/Tg) [58] (N07) CO + O3 $ \Rightarrow$ CO2 + O2 4.0 × 10–31 [52] (N08) CO2 + CO2 $ \Rightarrow$ CO + O + CO2 3.91 × 10–16exp(–49430/Tg) [59] (N09) C + CO + CO2 $ \Rightarrow$ C2O + CO2 6.3 × 10–44 [59] (N10) C2O + O $ \Rightarrow$ 2CO 5.0 × 10–17 [18] (N11) C2O + O2 $ \Rightarrow$ CO2 + CO 3.3 × 10–19 [18] (N12) O + O2 + CO2 $ \Rightarrow$ O3 + CO2 1.7 × 10–42Tg–1.2 [48] (N13) O + O + CO2 $ \Rightarrow$ O2 + CO2 3.81 × 10–42Tg–1exp(–170/Tg) [48] (N14) O + CO + CO2 $ \Rightarrow$ 2CO2 1.6 × 10–45exp(–1510/Tg) [48] (N15) O + CO + CO $ \Rightarrow$ CO2 + CO 6.54 × 10–45 [60] (N16) O + O2 + CO $ \Rightarrow$ CO2 + O2 6.51 × 10–48 [60] (N17) O + O + CO $ \Rightarrow$ O2 + CO 2.76 × 10–46 [60] (N18) O + O + O $ \Rightarrow$ O2 + O 6.2 × 10–44exp(–750/Tg) [52] (N19) O + O + O2 $ \Rightarrow$ 2O2 1.3 × 10–44(Tg/300)–1exp(–170/Tg) [52] (N20) O + O3 $ \Rightarrow$ 2O2 3.1 × 10–20Tg0.75exp(–1575/Tg) [18] (N21) O2 + O3 $ \Rightarrow$ 2O2 + O 7.26 × 10–16exp(–11400/Tg) [48] (N22) O2 + O + O2 $ \Rightarrow$ O3 + O2 8.61 × 10–43Tg–1.25 [48] (N23) O2 + O2 $ \Rightarrow$ O + O3 2.1 × 10–17exp(–498000/Tg) [57] (N24) O2 + M $ \Rightarrow$ O + O + M 3.0 × 10–12Tg–1exp(–59380/Tg) [57]
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表 B2 简化集合中由碰撞截面描述的电子碰撞反应
Table B2. Electron impact reactions described by collision cross sections in the simplified model.
序号 反应 文献 序号 反应 文献 (Y01) e + CO2 $\Rightarrow $ $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + 2e [50] (Y11) e + O3 $\Rightarrow $ $ {\mathrm{O}}_{2}^{-} $ + O [50] (Y02) e + CO2 $\Rightarrow $ CO + O + e [50] (Y12) e + O3 $\Rightarrow $ O2 + O– [50] (Y03) e + CO2 $\Rightarrow $ CO + O– [50] (Y13) e + O3 $\Rightarrow $ O + O2 + e [53] (Y04) e + CO2 $\Rightarrow $ 2e + O + CO+ [50] (Y14) e + O3 $\Rightarrow $ $ {\mathrm{O}}_{2}^{+} $ + O + 2e [53] (Y05) e + CO2 $\Rightarrow $ 2e + CO + O+ [50] (Y15) e + O2 $\Rightarrow $ 2 O + e [50] (Y06) e + CO2 $\Rightarrow $ $ {\mathrm{O}}_{2}^{+} $ + C + 2e [51, 52] (Y16) e + O2 $\Rightarrow $ O + O– [50] (Y07) e + CO $\Rightarrow $ C + O– [50] (Y17) e + O2 $\Rightarrow $ 2e + $ {\mathrm{O}}_{2}^{+} $ [50] (Y08) e + CO $\Rightarrow $ e + C + O [50] (Y18) e + O $\Rightarrow $ 2e + O+ [50] (Y09) e + CO $\Rightarrow $ 2e + CO+ [50] (Y19) e + C $\Rightarrow $ 2e + C+ [50] (Y10) e + CO $\Rightarrow $ 2e + C+ + O [50]
DownLoad: CSV
表 B3 简化集合中由反应速率系数描述的电子碰撞反应, 其中Te为电子温度, 单位是eV; Tg为气体温度, 单位是K; 速率系数的单位在二体或三体反应中分别是m3/s或m6/s
Table B3. Electron impact reactions described by rate coefficients in the simplified model. Te is the electron temperature in eV and Tg is the gas temperature in K. The rate coefficients are in m3/s or m6/s for binary or ternary reactions.
序号 反应 反应速率系数 文献 (F01) e + $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ $\Rightarrow $ C + O2 3.94 × 10–13Te–0.4 [21] (F02) e + $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ $\Rightarrow $ CO + O 2.0 × 10–11Te–0.5Tg–1 [18] (F03) e + O3 + O2 $\Rightarrow $ $ {\mathrm{O}}_{3}^{-} $ + O2 4.6 × 10–40 [52] (F04) e + $ {\mathrm{O}}_{2}^{+} $ $\Rightarrow $ 2O 6.0 × 10–13Te–0.5(1/Tg)0.5 [21]
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表 B4 简化集合中的中性粒子反应, 其中, Tg 为气体温度, 单位是 K; 速率系数的单位在二体或三体反应中分别是 m3/s 或 m6/s
Table B4. Reaction of neutrals in the simplified model. Tg is the gas temperature in K. The rate coefficients are in m3/s or m6/s for binary or ternary reactions.
DownLoad: CSV
表 B5 简化集合中的离子-中性和离子-离子反应, 其中Tg为气体温度, 单位是K; 速率系数的单位在二体或三体反应中分别是m3/s或m6/s
Table B5. Ion-neutral and ion-ion reactions in the simplified model. Tg is the gas temperature in K. The rate coefficients are in m3/s or m6/s for binary or ternary reactions.
序号 反应 反应速率系数 文献 (H01) O– + CO2 $ \Rightarrow $ O + CO2 + e 4.0 × 10–18 [48] (H02) O– + CO2 + CO $ \Rightarrow $ $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + CO 1.5 × 10–40 [61] (H03) O– + CO2 + O2 $ \Rightarrow $ $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + O2 3.1 × 10–40 [61] (H04) O– + CO2 + CO2 $ \Rightarrow $ $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + CO2 9.0 × 10–41 [52] (H05) $ {\mathrm{O}}_{2}^{-} $ + CO2 + O2 $ \Rightarrow $ $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ + O2 4.7 × 10–41 [52] (H06) $ {\mathrm{O}}_{3}^{-} $ + CO2 $ \Rightarrow $ $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + O2 5.5 × 10–16 [18] (H07) O+ + CO2 $ \Rightarrow $ $ {\mathrm{O}}_{2}^{+} $ + CO 9.4 × 10–16 [18] (H08) O+ + CO2 $ \Rightarrow $ O + $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ 4.5 × 10–16 [18] (H09) C+ + CO2 $ \Rightarrow $ CO+ + CO 1.1 × 10–15 [18] (H10) CO+ + CO2 $ \Rightarrow $ $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + CO 1.0 × 10–15 [56] (H11) O– + CO $ \Rightarrow $ CO2 + e 5.5 × 10–16 [44] (H12) $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + CO $ \Rightarrow $ 2CO2 + e 5.0 × 10–19 [58] (H13) $ {\mathrm{O}}_{2}^{+} $ + C $ \Rightarrow $ CO+ + O 5.2 × 10–17 [18] (H14) $ {\mathrm{O}}_{2}^{+} $ + C $ \Rightarrow $ C+ + O2 5.2 × 10–17 [18] (H15) O– + C $ \Rightarrow $ CO + e 5.0 × 10–16 [57] (H16) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + O $ \Rightarrow $ $ {\mathrm{O}}_{2}^{+} $ + CO 1.638 × 10–16 [52] (H17) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + O $ \Rightarrow $ CO2 + O+ 9.62 × 10–17 [18] (H18) $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ + O $ \Rightarrow $ $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + O2 1.1 × 10–16 [18] (H19) $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ + O $ \Rightarrow $ CO2 + O2 + O– 1.4 × 10–17 [18] (H20) $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ + O $ \Rightarrow $ CO2 + $ {\mathrm{O}}_{3}^{-} $ 1.4 × 10–16 [18] (H21) $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + O $ \Rightarrow $ CO2 + $ {\mathrm{O}}_{2}^{-} $ 8.0 × 10–17 [58] (H22) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + O2 $ \Rightarrow $ $ {\mathrm{O}}_{2}^{+} $ + CO2 6.4 × 10–17 [52] (H23) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + O– $ \Rightarrow $ O + CO2 1.0 × 10–13 [62] (H24) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + $ {\mathrm{O}}_{2}^{-} $ $ \Rightarrow $ CO + O2 + O 6.0 × 10–13 [44] (H25) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ $ \Rightarrow $ 2CO2 + O 5.0 × 10–13 [58] (H26) $ {\mathrm{C}\mathrm{O}}_{2}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ $ \Rightarrow $ 2CO2 + O2 5.0 × 10–13 [18] (H27) $ {\mathrm{C}\mathrm{O}}_{3}^{-} $ + $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow $ CO2 + O2 + O 3.0 × 10–13 [18] (H28) $ {\mathrm{O}}_{2}^{+} $ + $ {\mathrm{C}\mathrm{O}}_{4}^{-} $ $ \Rightarrow $ CO2 + 2O2 3.0 × 10–13 [18] (H29) O– + O3 $ \Rightarrow $ 2O2 + e 3.0 × 10–16 [44] (H30) O– + O3 $ \Rightarrow $ $ {\mathrm{O}}_{3}^{-} $ + O 8.0 × 10–16 [18] (H31) $ {\mathrm{O}}_{2}^{-} $ + O3 $ \Rightarrow $ $ {\mathrm{O}}_{3}^{-} $ + O2 4.0 × 10–16 [18] (H32) O– + O2 $ \Rightarrow $ O + e + O2 6.9 × 10–16 [52] (H33) O– + O $ \Rightarrow $ O2 + e 2.3 × 10–16 [21] (H34) $ {\mathrm{O}}_{2}^{-} $ + O $ \Rightarrow $ O2 + O– 3.31 × 10–16 [21] (H35) $ {\mathrm{O}}_{2}^{-} $ + O $ \Rightarrow $ O3 + e 3.3 × 10–16 [18] (H36) $ {\mathrm{O}}_{3}^{-} $ + O $ \Rightarrow $ $ {\mathrm{O}}_{2}^{-} $ + O2 2.5 × 10–16 [18] (H37) O–+ $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow $ O2 + O 2.6 × 10–14(300/Tg)0.44 [21] (H38) O– + $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow $ 3O 4.2 × 10–13(300/Tg)0.44 [21] (H39) $ {\mathrm{O}}_{2}^{-} $ + $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow $ 2O2 2.01 × 10–13(300/Tg)0.5 [21] (H40) $ {\mathrm{O}}_{2}^{-} $ + $ {\mathrm{O}}_{2}^{+} $ $ \Rightarrow $ O2 + 2O 4.2 × 10–13 [21]
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