Pseudoelementary Steps: A Key Concept and Tool for Studying the Kinetics and Mechanisms of Complex Chemical Systems.

The concept of a pseudoelementary step (PEStep) is reviewed, a key concept for approaching the analysis of kinetics data and associated, underlying mechanisms of complex chemical systems. Following a brief Introduction, a definition of a PEStep is given: a PEStep is an initial building block for more complex reactions , that is a starting point for the initial analysis of the observed kinetics and then constructing initial, deliberately minimalistic mechanistic models for complex reactions. PESteps are, therefore and typically, composites of underlying elementary step reactions and can be very useful if not required for the inverse problem of discovering mechanisms from experimental observables for complex reactions. It is the use of PESteps in the inverse problem of mechanism determination that is a primary focus of this review. After a section detailing the results of a literature search of "pseudoelementary step" and related terms such as "pseudoelementary process", pedagogically illustrative examples are given of the use of the PEStep concept in approaching and elucidating the mechanisms of complex reactions. This review shows how the underlying elementary steps of a catalytic cycle were successfully uncovered via a PEStep approach, addresses the classic case of the use of PESteps in determining the mechanisms of oscillating reactions, and examines a well-studied case of an Ir(0) n nanoparticle formation reaction. This latter example is illustrative in that the Ir(0) n nanoparticle formation reaction consisting of thousands of underlying elementary steps that, however, can be treated initially kinetically as just two PESteps, a reduction in complexity of 3 orders of magnitude. Known weaknesses and caveats of the PEStep approach are also summarized and discussed. A short summary of Horituti's "Stoichiometric Number" concept is provided, a concept that would appear to merit further investigation and use in the study of complex reactions. Finally, a section is provided that lists a few, selected areas where the PEStep concept and methodology are expected to prove especially important in the future, and a Conclusions section is provided that lists 11 bullet points. The latter serves as a summary of this first review of the PEStep concept and its importance in dealing with the kinetics and in elucidating the mechanisms of more complex, multistep reactions.