Dynamics Simulations and Statistical Modeling of Thermal Decomposition of 1-Ethyl-3-methylimidazolium Dicyanamide and 1-Ethyl-2,3-dimethylimidazolium Dicyanamide.

摘要

Quasi-classical, direct dynamics trajectories were calculated at the B3LYP/6-31G* level of theory, in an attempt to understand decomposition mechanisms of 1-ethyl-3-methylimidazolium dicyanamide (EMIM+DCA-) and 1-ethyl-2,3-dimethylimidazolium dicyanamide (EMMIM+DCA-). The trajectories, simulated at 4000 K, showed many dissociation paths for these two ionic liquids. Using trajectory results as a guide, structures of transition states and products that might be important for decomposition of these two compounds were determined using density functional theory calculations. Rice-Ramsperger-Kassel-Marcus (RRKM) theory was then utilized to examine properties of energized ionic liquids and to determine unimolecular rates for crossing various transition states. On the basis of RRKM modeling, initial decomposition paths for energized EMIM+DCA- correspond to formation of an N-heterocyclic carbene via transfer of the C2 proton of EMIM+ to DCA-, and evolution of methylimidazole and ethylimidazole via SN2 alkyl abstraction by DCA-. Similar decomposition paths were identified for energized EMMIM+DCA-, except that the reactivity of C2 of the imidazolium cation is significantly reduced upon substitution of a methyl group for a hydrogen atom at this position. The present work demonstrates that dynamics simulations, in conjunction with statistical modeling, are able to provide great insight into decomposition mechanisms, kinetics and dynamics for alkylimidazolium-based ionic liquids, and predict product branching ratios and how they vary with decomposition temperatures.