Abstract
While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.
Highlights
Complex reaction mechanisms, in which many competing reaction steps combine to form a network of chemical reactions, are increasingly recognized as a common pattern in chemistry.[1,2] Characteristic features of complex reactions include branching and interference of reaction pathways, autocatalysis, and product inhibition and are observed in systems as varied as transition-metal catalysis,[3] cell metabolism,[4,5] and polymerization.[1,6,7] A better understanding of the network effects in these complex reactions offers means for influencing their dynamics and product composition
Guided by the above expectation, we propose a computational framework of heuristics-aided quantum chemistry (HAQC) suitable for exploring complex and large-scale reaction mechanisms
We present models of the formose reaction in different stoichiometries obtained using a combination of chemical heuristics and semiempirical quantum chemistry (Section 3)
Summary
In which many competing reaction steps combine to form a network of chemical reactions, are increasingly recognized as a common pattern in chemistry.[1,2] Characteristic features of complex reactions include branching and interference of reaction pathways, autocatalysis, and product inhibition and are observed in systems as varied as transition-metal catalysis,[3] cell metabolism,[4,5] and polymerization.[1,6,7] A better understanding of the network effects in these complex reactions offers means for influencing their dynamics and product composition Useful contributions to this effort can be expected from theoretical works, which are capable of providing accurate predictions of molecular structures and reactivities.
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