Autocatalytic reaction mechanisms are observed in a range of important chemical processes including catalysis, radical-mediated explosions, and biosynthesis. Because of their complexity, the microscopic details of autocatalytic reaction mechanisms have been difficult to study on surfaces and heterogeneous catalysts. Autocatalytic decomposition reactions of S,S-and R,R-tartaric acid (TA) adsorbed on Cu(110) offer molecular-level insight into aspects of these processes, which until now, were largely a matter of speculation. The decomposition of TA/Cu( 110) is initiated by a slow, irreversible process that forms vacancies in the adsorbed TA layer, followed by a vacancy-mediated, explosive decomposition process that yields CO 2 and small hydrocarbon products. Initiation of the explosive decomposition of TA/Cu(110) has been studied by measurement of the reaction kinetics, time-resolved low energy electron diffraction (LEED), and time-resolved scanning tunneling microscopy (STM). Initiation results in a decrease in the local coverage of TA and a concomitant increase in the areal vacancy concentration. Observations of explosive TA decomposition on the Cu(651) S surface suggest that initiation does not occur at structural defects in the surface, as has been suggested in the past. Once the vacancy concentration reaches a critical value, the explosive, autocatalytic decomposition step dominates the TA decomposition rate. The onset of the explosive decomposition of TA on Cu(110) is accompanied by the extraction of Cu atoms from the surface to form a (±6,7; ∓2,1) overlayer that is readily observable using LEED and STM. The explosive decomposition step is second-order in vacancy concentration and accelerates with increasing extent of reaction.

Chiral inorganic materials predated life on Earth, and their enantiospecific surface chemistry may have played a role in the origins of biomolecular homochirality. However, enantiospecific differences in the interaction energies of chiral molecules with chiral surfaces are small and typically lead to modest enantioselectivities in adsorption, catalysis, and chemistry on chiral surfaces. To yield high enantioselectivities, small energy differences must be amplified by reaction mechanisms such as autocatalytic surface explosions which have nonlinear kinetics. Herein, we report the first observations of superenantiospecificity resulting from an autocatalytic surface explosion reaction of a chiral molecule on a naturally chiral surface. R,R- and S,S-tartaric acid decompose via a vacancy-mediated surface explosion mechanism on Cu single crystal surfaces. When coupled with surface chirality, this leads to decomposition rates that exhibit extraordinarily high enantiospecificity. On the enantiomorphs of naturally chiral Cu(643)(R&S), Cu(17,5,1)(R&S), Cu(531)(R&S) and Cu(651)(R&S) single crystal surfaces, R,R- and S,S-tartaric acid exhibit enantiospecific decomposition rates that differ by as much as 2 orders of magnitude, despite the fact that the effective rates constants for decomposition differ by less than a factor of 2.

Aspartic acid adsorbed on Cu surfaces is doubly deprotonated. On chiral Cu(643) its enantiomers undergo enantiospecific decomposition via an autocatalytic explosion. Once initiated, the decomposition mechanism proceeds via sequential cleavage of the C3-C4 and C1-C2 bonds each yielding CO, followed by conversion of the remaining species into N[triple bond, length as m-dash]CCH.

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