HCl dissociation on noble metals: A model system for electronically nonadiabatic interactions in chemical reactions at metal surfaces

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Born-Oppenheimer failure is well established as an important influence in the transfer of energy from an energized molecule to a metal solid. Yet, there are still no experimental demonstrations that these effects influence chemical reaction probabilities. We propose experiments on HCl dissociation on Au(111), a reaction system where Born-Oppenheimer failure is known to be important for vibrationally inelastic scattering and where Born-Oppenheimer failure is also likely to influence the dissociation probability. Our aim is for these studies to become a benchmark example of Born-Oppenheimer failure in a simple chemical reaction occurring at a metal surface, one that can provide incentive to develop more advanced theories of surface chemistry that include the effects of Born-Oppenheimer failure.