Observation of orientation-dependent electron transfer in molecule-surface collisions

Molecules typically must point in specific relative directions to participate efficiently in energy transfer and reactions. For example, Forster energy transfer favors specific relative directions of each molecule's transition dipole [Forster T (1948) Ann Phys 2(1-2):55-75] and electron transfer between gas- phase molecules often depends on the relative orientation of orbitals [Brooks PR, et al. (2007) J Am Chem Soc 129(50):15572-15580]. Surface chemical reactions can be many orders of magnitude faster than their gas-phase analogs, a fact that underscores the importance of surfaces for catalysis. One reason surface reactions can be so fast is the labile change of oxidation state that commonly takes place upon adsorption, a process involving electron transfer between a solid metal and an approaching molecule. By transferring electrons to or from the adsorbate, the process of bond weakening and/or cleavage is initiated, chemically activating the reactant [Yoon B, et al. (2005) Science 307(5708):403-407]. Here, we show that the vibrational relaxation of NO-an example of electronically nonadiabatic energy transfer that is driven by an electron transfer event [Gadzuk JW (1983) J Chem Phys 79(12):6341-6348]-is dramatically enhanced when the molecule approaches an Au(111) surface with the N atom oriented toward the surface. This represents a rare opportunity to investigate the steric influences on an electron transfer reaction happening at a surface.