This study employs a multiscale theoretical approach to systematically investigate the thermal stability, phase transition characteristics, and pyrolysis product distributions of four long-chain n-alkanes ranging from n-dodecane to n-pentadecane (C12–C15). At the electronic structure level, density functional theory calculations reveal that with increasing chain length, the HOMO–LUMO gap narrows monotonically from 8.87 eV to 8.77 eV and global softness increases, indicating enhanced electronic responsiveness to thermal perturbation. Molecular electrostatic potential analysis shows decreasing surface potential variance and 100% nonpolar surface area across all species, confirming that intermolecular interactions are exclusively governed by London dispersion forces. At the condensed-phase level, semiempirical quantum-based molecular dynamics (xTB-MD) simulations at 3500 K over 6 ps trajectories reveal qualitative chain-length-dependent initial bond-breaking patterns: C2 species appear prominently among early fragments for C12–C15 systems, with medium-sized fragments (C3, C4) becoming increasingly prevalent and C1 species relatively less prominent as chain length grows. This work provides an integrated “electronic structure-condensed phase transition-pyrolysis kinetics” perspective, offering precise theoretical insights and critical benchmark data for the pyrolysis mechanisms of long-chain n-alkanes.
Ke et al. (Wed,) studied this question.