Hints to lightning breakdown enhancement for synthetic ester insulating oil: Unraveling the impact of molecular chain length on electron structural parameters under electric field stress

The high flash point and biodegradability of synthetic ester insulating oil offer transformers both operational stability and environmental protection. However, its poor lightning breakdown characteristics under long oil gaps and inhomogeneous electric field often lead to rapid streamer discharges, posing challenges and limits to the use of synthetic ester insulating oil and hinders the development of low-carbon, eco-friendly high voltage power transformers. To address this issue, we propose improving the lightning breakdown characteristics through molecular chain length design. Using density functional theory, time-dependent density functional theory, and wave function analysis, we investigate how microscopic factors like molecular polarity, discharge active sites, frontier orbitals, traps, ionization and electron affinity, and excitation processes influence macroscopic discharge characteristics. Our findings show that under an electric field, chain length is positively correlated with electron transfer, enhancing charge polarization. Chain length also correlates positively with dipole moment, facilitating the formation of space charge centers. While chain length minimally affects discharge active sites, the electric field can intensify their formation. Additionally, a longer chain length decreases the energy gap, increasing electron trap levels more than hole trap levels, thus capturing charges longer. Chain length is negatively correlated with ionization energy, promoting electron impact ionization, and has little effect on the excitation energy of S(0) → S(1), making excitation under high electric fields unlikely.