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We report density functional theory calculations of electron-hole pair induced vibrational lifetimes of diatomic molecules adsorbed on metal surfaces. For CO on Cu (100), Ni (100), Ni (111), Pt (100), and Pt (111), we find that the C–O internal stretch and the bending modes have lifetimes in the 1–6 ps range, and that the CO-surface stretch and the frustrated translational modes relax more slowly, with lifetimes> 10 ps for all cases except CO on Ni (111). This strong mode selectivity confirms earlier calculations for CO on Cu (100) and demonstrates that the trends carry over to other metal substrates. In contrast, for NO adsorbed on Pt (111), whereas we still find that the bending mode has the shortest lifetime, about 1.3 ps⁠, we predict the other three modes to have almost equal lifetimes of 8–10 ps⁠. Similarly, for CN adsorbed on Pt (111), we calculate that the internal stretching and molecule-surface stretching modes …