To promote noncovalent irreversible bimolecular complex design, this article reports 72 distinct pathways of the noncovalent self-assembly of neocarcerand Octacid4 (Fig. ) with three known guests-1,4-dioxane (dioxane), p-xylene (xylene), and naphthalene . These pathways were captured in multiple distinct, independent, unrestricted, unbiased, and classical isobaric-isothermal molecular dynamics (MD) simulations at a high time resolution with an aggregated simulation time exceeding 2.942592 milliseconds at 298-363 K, rendering the structural and kinetic information needed to answer the two high-level questions and guide the design of noncovalent irreversible complexes that can be formed in situ and adiabatically with desired kinetics for materials technology, data storage and processing, molecular sensing and tagging, and drug therapy.