Density functional study of relaxation of adsorbate vibration modes: Dominance of anharmonic interaction.

Formulation and density functional workflow for calculating the lifetime of vibrational modes of molecular adsorbates on solid surfaces due to vibration-phonon coupling are presented. The anharmonic coupling is invoked to give the correct description of the origin of temperature dependence. Using pyrrolidine (CHN) absorbed on the Cu(001) surface as a concrete example, we show that the anharmonic coupling can be one to two orders more significant than the harmonic interaction for the broadening of vibrational spectra, especially as temperature increases. These results challenge the common assumption that the anharmonic interaction is weak and call for attention of considering its effect in quantum relaxation and related problems.