Mechanism and Energetics of Hydrogen Sulfide Thermolysis from Reactive Molecular Dynamics: Cutoff-Radius Effects, Thermochemically Validated Energy Costs, and the Elementary Reaction Network

Hydrogen sulfide (H2S), a high-volume by-product of the hydrodesulfurization of fossil fuels, can be valorized by thermolysis to recover both molecular hydrogen and elemental sulfur, rather than being oxidized as in the conventional Claus process. The viability of this route depends on quantitative knowledge of the reaction mechanism and of the energy costs of dissociation, which are difficult to obtain experimentally at the temperatures involved. Here we study H2S thermolysis by reactive molecular dynamics (RMD) with the ReaxFF potential for systems of 1000 H2S molecules at 1 atm, addressing three coupled questions: the simulation parameters required for dilute gases, the energetics of dissociation, and the elementary reaction mechanism. The interaction cutoff radius proved critical: the original 10 Å value, parametrized for condensed systems, misses about 23 eV of attractive non-bonded interaction energy in the gaseous system at 298.15 K (≈0.023 eV per molecule) and fails to capture dissociation at 3000 K within 20 ns, whereas radii of 30–40 Å converge. Using a 40 Å cutoff at 2500, 3000 and 3500 K, atom-resolved species-transition records reveal a free-radical chain mechanism built from the same set of elementary steps at the three temperatures, whose relative contributions shift with temperature: S–H homolysis initiates the chain, hydrogen abstraction (H• + H2S → H2 + HS•) is essentially the exclusive source of H2 (persistent H• + H• recombination contributed only 1, 13 and 17 events, below 0.5% of the abstraction count), and a slow sulfur-condensation stage (S2 → S3 → S4) limits the net conversion, which reached 9.3 ± 0.9%, 26.3 ± 1.4% and 46.7 ± 1.6% within the simulated windows (single-trajectory counting resolution)—kinetically limited values, not equilibrium conversions. The enthalpy of the system rises linearly with the number of H2S molecules consumed (R2 ≥ 0.99), defining energy costs of 2.46 ± 0.04, 3.10 ± 0.08 and 3.95 ± 0.18 eV per molecule that increase with temperature by ≈1.48 eV per 1000 K; at 3500 K the cost lies between the 0 K complete-dissociation limit D0 = 3.90 eV derived from the experimental H–SH bond energy and the Kirchhoff-corrected complete-dissociation enthalpy at that temperature (4.11–4.12 eV), statistically indistinguishable from the latter (a 0.9σ difference). These results provide a thermochemically validated, molecular-level basis for engineering the valorization of residual H2S as a source of green hydrogen.