High-Temperature Decomposition Characteristics and Mechanism of Environmentally Friendly Insulating Gas PMVE at the Molecular Scale

Perfluoromethyl vinyl ether (PMVE) is an environmentally friendly insulating gas that has garnered significant attention for its potential in high-voltage applications. Despite its promise, challenges remain in understanding its chemical reactivity, decomposition characteristics, and the insulation properties of its decomposition products under varying conditions. This study addresses these gaps using a multi-faceted theoretical approach. First, density functional theory is employed to calculate PMVE’s ionization energy, electron affinity, molecular orbitals, and bond levels, revealing its chemical reactivity from a molecular perspective. Second, reactive molecular dynamics simulations are conducted to investigate the decomposition rate of PMVE, the types of free radicals and molecules produced, and the distribution of main products at different temperatures. Finally, thermodynamic analysis elucidats the reaction difficulty and formation pathways of the primary decomposition products. The results indicate that PMVE decomposition accelerates with increasing temperature, with initial bond cleavages occurring at the C2-O, C2-F3, and C3-O bonds, forming reactive intermediates such as C2F3·, COF3·, CF3·, and C2OF3·. Further reactions yield products including C2F2, C2F4, COF2, CO, C2F6, C3F6, and CF4. These findings align with experimental data and confirm that the decomposition products retain excellent insulation properties, supporting PMVE’s suitability for engineering applications. This work provides critical theoretical insights and guidance for the practical implementation of PMVE in insulation systems.