Disentangling Multidimensional Nonequilibrium Dynamics of Adsorbates: CO Desorption from Cu(100).

Two-dimensional infrared surface spectroscopy for CO on Cu(100): detection of intermolecular coupling of adsorbates.

Surface-specific infrared signals obtained by subjecting the system to two infrared laser pulses are calculated for an admixture of CO and isotopic CO on Cu(100) by using molecular dynamics simulation based on a stability matrix formalism. The two-dimensional profiles of the signals in the frequency domain show both diagonal and cross peaks. The former peaks mainly arise from the overtones of t...

Quantum corrected Langevin dynamics for adsorbates on metal surfaces interacting with hot electrons.

We investigate the importance of including quantized initial conditions in Langevin dynamics for adsorbates interacting with a thermal reservoir of electrons. For quadratic potentials the time evolution is exactly described by a classical Langevin equation and it is shown how to rigorously obtain quantum mechanical probabilities from the classical phase space distributions resulting from the dy...

Probing surface short range order and inter-adsorbate interactions through IR vibrational spectroscopy: CO on Cu(100).

It is demonstrated that surface vibrational spectroscopy can be used to probe local ordering of adsorbates and the nature of inter-adsorbate interactions through dynamical dipole coupling among neighboring adsorbates. Our studies show that for CO adsorbed on Cu(100), first and second nearest neighbor interactions are repulsive. This repulsion prevents the formation of long range ordered structu...

Title Two-dimensional infrared surface spectroscopy for CO on Cu(100): Detection of intermolecular coupling of adsorbates

Instantaneous vibrational frequencies of diffusing and desorbing adsorbates: CO/Pt(111).

Electronic excitation of metal by intense laser pulses stimulates nuclear motions of adsorbates through nonadiabatic coupling, resulting in diffusion and desorption of adsorbates. These processes take place via precursor states: adsorbates whose vibrational modes with respect to substrate are highly excited. This paper reports the dynamics of precursor states of CO on Pt(111) probed by use of i...