Theoretical Study on the Polymerization Mechanism of Hydrogen-Doped Carbon Monoxide under High Pressure
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摘要: 一氧化碳（CO）是典型的低原子序数（Z）体系，能够在高压下通过聚合反应形成聚一氧化碳（p-CO），其高压聚合机理与结构对于理解压力诱导成键机制和探索新型功能材料具有重要价值，但是相关研究受到CO聚合压力偏高和产物p-CO在常压下具有亚稳态特性两方面阻碍。目前，人们发现氢气（H2）掺杂有助于CO聚合，但是对相应的聚合机理和产物结构缺乏认知，为此，利用分子动力学方法研究了H2掺杂对CO高压聚合机理的影响规律。结果表明，摩尔分数为10%的H2掺杂具有降低CO聚合压力的最优效果。当压力为3～4 GPa时，H2通过物理作用促进了CO的二聚化；当压力提高到5 GPa时，H2由于化学惰性阻碍了体系的进一步聚合；当压力提高到10 GPa时，H2能够参与聚合反应，产生C―H键和O―H键。最终，聚合反应会形成一个无序、以C―C键和C＝O键为主的三维网状结构p-CO/H。Abstract: Carbon monoxide (CO), as a prototypical low-Z molecular system, can polymerize under high pressure to form polymeric carbon monoxide (p-CO). The polymerization mechanisms and structures are of fundamental importance for understanding pressure-induced bonding and exploring novel functional materials. However, progress in this field has been hindered by two major challenges: the high-pressure requirements for CO and the metastable property of p-CO at ambient pressure. Recent studies have shown that hydrogen (H2) doping can facilitate the polymerization of CO, but the polymerization mechanisms and structures are still poorly understood. In this work, molecular dynamics simulations were performed to investigate the influence of H2 on the polymerization progress of CO. The results reveal that a doping ratio of 10% can optimally reduce the polymerization pressure of CO. At 3–4 GPa, H2 physically induces the dimerization reaction of CO. At 5 GPa, the chemical inertness of H2 inhibits further polymerization of CO. When the pressure reaches 10 GPa, H2 participates in the polymerization reaction, forming C―H and O―H bonds. Finally, the polymerization produces a disordered three-dimensional network structure (p-CO/H) dominated by C―C and C＝O bonds.
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Key words:
- carbon monoxide /
- hydrogen /
- high-pressure polymerization /
- molecular dynamics
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图 1 不同H2摩尔分数的H2/CO混合体系结构模型（褐色球为C，红色球为O，白色球为H）
Figure 1. Structural models of H2/CO mixed systems with different H2 molar ratios (The brown, red and white balls denote C, O and H atoms, respectively.)
图 3 3 GPa下、充分弛豫后不同H2摩尔分数的H2/CO混合体系结构（褐色球为C，红色球为O，白色球为H；红圈表示CO寡聚体；为简洁起见，隐藏了H―H键）
Figure 3. Structural models of H2/CO mixed systems with different H2 molarratios under 3 GPa (The brown, red and white balls denote C, O and H atoms, respectively; the red circle indicates CO oligomer; the H―H bonds are omitted for clarity.)
图 4 4 GPa下、充分弛豫后不同H2摩尔分数的H2/CO混合体系结构（褐色球为C，红色球为O，白色球为H；红圈表示CO寡聚体；为简洁起见，隐藏了H―H键）
Figure 4. Structural models of H2/CO mixed systems with different H2 molarratios under 4 GPa (The brown, red and white balls denote C, O and H atoms, respectively; the red circle indicates CO oligomer; the H―H bonds are omitted for clarity.)
图 5 4 GPa下不同H2摩尔分数的H2/CO混合体系C-C原子对的RDF（实线）曲线和CN（点线）曲线
Figure 5. RDF (solid) curves and CN (dot) curves of C-C pairs for H2/CO mixed systems with different H2 molar ratios under 4 GPa
图 6 纯CO体系和10% H2掺杂CO体系（插图）二聚化反应过程中的自由能曲线（插图中的红色虚线为用于计算自由能设置的集体变量）
Figure 6. Free energy curves during the dimerization reaction in both pure CO and 10% H2-doped CO systems (inset) (The red dashed line in the inset represents the collective variable defined for the free energy calculation.)
图 7 纯CO体系和10% H2掺杂CO体系中CO分子的均方根位移
Figure 7. RMSD of CO molecules in pure CO and 10% H2-doped COsystems
图 8 10% H2掺杂CO体系在5 和10 GPa压力下的结构模型、物种数和化学键数量演化（褐色球为C，红色球为O，白色球为H）
Figure 8. Structural models, evolution of species and chemical bonds of the mixed CO system with 10% H2 under 5 and 10 GPa (Brown, red and white balls denote C, O and H atoms, respectively.)
图 9 10 GPa压力下10% H2掺杂CO体系中与H2相关的化学反应以及形成的H键（褐色球为C，红色球为O，白色球为H，波浪线表示与聚合网络连接的化学键）
Figure 9. Chemical reactions involved in H2 and H-bonds in the mixed system under 10 GPa (Brown, red and white balls denote C, O and H atoms, respectively. The wavy lines represent the chemical bonds connected to the aggregated network.)
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