Erratum: Theory of vibrational equilibria and pooling at solid-diatom interfaces [J. Chem. Phys. 139, 124107 (2013)]

The Sommerfeld ground-wave limit for a molecule adsorbed at a surface

“…The red curve in Fig. 2A shows a kMC simulation under our experimental conditions where only nearest-neighbor V-V energy transfer is permitted, an assumption used in previous work (14)(15)(16)(17)(18). This approach yields a peak in population at v ~8 (base-camp 1), strongly resembling figure 3 of ( 14) and ( 15) but markedly different from experiment.…”

“…The solid squares in Fig. 4B are the effective lifetimes that result from implementation of the Skinner-Tully (ST) model (14,24), where anharmonic coupling of CO vibration to NaCl phonons is mediated via the CO-NaCl surface bond (14)(15)(16)(17)(18). The predicted effective lifetimes are in poor agreement with experiment, and they exhibit a vibrational quantum number dependence that is far too strong.…”

“…The insets represent the CO lattice; the red shaded areas visualize the interaction distance around a given CO molecule (black dot) used in each kMC simulation. In (A), the simulation allows only nearest-neighbor V-V exchange, an assumption that was also made in (14)(15)(16). In (B), the simulation includes molecular interactions out to a distance of 34 Å.…”