Abstract

Most chemical reactions occur over multiple steps whose identity is elucidated by experiment, yielding a reaction mechanism. Knowledge of cognitive science suggests that mechanism elucidation can be viewed as a knowledge-guided search within a combinatorial space. The MECHEM computer program searches this space comprehensively for the simplest plausible mechanisms. We use MECHEM to find mechanisms for Fischer-Tropsch chemistry and CO2 reforming of methane, both heterogeneous catalytic reactions of current importance. The results reveal hundreds of equally simple mechanisms consistent with evidence. Hence, mechanism elucidation in catalysis is a much harder problem than is ordinarily realized.

full paper