Probing the non-pairwise interactions between CO molecules moving on a Cu(111) surface.
ABSTRACT The coverage dependent dynamics of CO on a Cu(111) surface are studied on an atomic scale using helium spin-echo spectroscopy. CO molecules occupy top sites preferentially, but also visit intermediate bridge sites in their motion along the reaction coordinate. We observe an increase in hopping rate as the CO coverage grows; however, the motion remains uncorrelated up to at least 0.10 monolayers (ML). From the temperature dependence of the diffusion rate, we find an effective barrier of 98 ± 5 meV for diffusion. Thermal motion is modelled with Langevin molecular dynamics, using a potential energy surface having adsorption sites at top and bridge positions and the experimental data are well represented by an adiabatic barrier for hopping of 123 meV. The sites are not degenerate and the rate changes observed with coverage are modelled successfully by changing the shape of the adiabatic potential energy surface in the region of the transition state without modifying the energy barrier. The results demonstrate that sufficient detail exists in the experimental data to provide information on the principal adsorption sites as well as the energy landscape in the region of the transition state.
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ABSTRACT: Experimental observations suggest that molecular adsorbates exhibit a larger friction coefficient than atomic species of comparable mass, yet the origin of this increased friction is not well understood. We present a study of the microscopic origins of friction experienced by molecular adsorbates during surface diffusion. Helium spin-echo measurements of a range of five-membered aromatic molecules, cyclopentadienyl, pyrrole, and thiophene, on a copper(111) surface are compared with molecular dynamics simulations of the respective systems. The adsorbates have different chemical interactions with the surface and differ in bonding geometry, yet the measurements show that the friction is greater than 2 ps(-1) for all these molecules. We demonstrate that the internal and external degrees of freedom of these adsorbate species are a key factor in the underlying microscopic processes and identify the rotation modes as the ones contributing most to the total measured friction coefficient.The Journal of Chemical Physics 05/2013; 138(19):194710. · 3.12 Impact Factor
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ABSTRACT: Accurate experimental data of adsorbate potential energy landscapes are crucial as benchmarks for the evaluation of first-principles calculations. Here, we present a Bayesian method, analyzing the difference in forward and backward hopping rate in helium spin-echo measurements, that allows us to determine the binding-energy difference between two sites with unprecedented accuracy. Demonstrating the power of the method on the model system cyclopentadienyl/Cu(111), we find an energy difference between fcc and hcp hollow sites of (10.6±1.7) meV.02/2014; 89(12).