Dynamics of atomic adsorbates: hydrogen on Cu(111)

Abstract We have measured the absolute changes induced in the far infrared reflectivity by H and D atoms adsorbed on Cu(111). The strongest features in the spectra are the dipole forbidden parallel vibrational modes which give rise to anti-absorption peaks with an intensity almost 10 times higher than that of the dipole allowed perpendicular modes. The dynamics can be explained by excitation of electron-hole pairs in the substrate. The energy relaxation time of the parallel vibration is 1 ps, but the linewidth is larger by a factor of 10 probably due to lateral tunneling of the adsorbates and dephasing processes.

[1]  Langreth Energy transfer at surfaces: Asymmetric line shapes and the electron-hole-pair mechanism. , 1985, Physical review letters.

[2]  R. Tobin Vibrational linewidths of adsorbed molecules: Experimental considerations and results , 1987 .

[3]  Gwyn P. Williams,et al.  Low-frequency dynamics of CO/Cu breakdown of Born--Oppenheimer approximation , 1994 .

[4]  Williams,et al.  Adsorbate-substrate resonant interactions observed for CO on Cu(100) in the far infrared. , 1990, Physical review letters.

[5]  J. Nørskov,et al.  Quantum Motion of Chemisorbed Hydrogen on Ni Surfaces , 1983 .

[6]  E. Plummer,et al.  Chemisorption of atomic hydrogen on Cu(111) , 1983 .

[7]  H. W. Thompson,et al.  Advances in Spectroscopy , 1959 .

[8]  A. Baró,et al.  Vibrational modes of hydrogen adsorbed on Pt(111): Adsorption site and excitation mechanism , 1979 .

[9]  Chabal Electronic damping of hydrogen vibration on the W(100) surface. , 1985, Physical review letters.

[10]  Williams,et al.  Adsorbate-induced changes in the infrared reflectance and resistivity of metals. , 1993, Physical review. B, Condensed matter.

[11]  W. Brenig Optical phonons and delocalization in hydrogen overlayers: lattice dynamics without displacement coordinates , 1993 .

[12]  E. Heilweil,et al.  PICOSECOND TIME-RESOLVED ADSORBATE RESPONSE TO SUBSTRATE HEATING : SPECTROSCOPY AND DYNAMICS OF CO/CU(100) , 1994 .

[13]  Coupling of H vibration to substrate electronic states in Mo(100)-p(1 x 1)H and W(100)-p(1 x 1)H: Example of strong breakdown of adiabaticity. , 1988, Physical review. B, Condensed matter.

[14]  Langreth,et al.  Asymmetric line shapes and the electron-hole pair mechanism for adsorbed molecules on surfaces. , 1987, Physical review. B, Condensed matter.

[15]  S. Parker,et al.  The adsorption of atomic hydrogen on Cu(111) investigated by reflection-absorption infrared spectroscopy, electron energy loss spectroscopy and low energy electron diffraction , 1989 .

[16]  Persson Reply to "Comment on 'Surface resistivity and vibrational damping in adsorbed layers' " , 1991, Physical review. B, Condensed matter.

[17]  M. Persson,et al.  Electronic Damping of Atomic and Molecular Vibrations at Metal Surfaces , 1984 .

[18]  A. Volokitin,et al.  Infrared reflection-absorption spectroscopy of dipole-forbidden adsorbate vibrations , 1993 .

[19]  Yinggang Li,et al.  Nonadiabatic effects in hydrogen diffusion in metals , 1992 .

[20]  W. Ho,et al.  Angle‐resolved and variable impact energy electron vibrational excitation spectroscopy of molecules adsorbed on surfaces , 1980 .

[21]  J. Nørskov,et al.  Chemisorption and vibration of hydrogen on Cu(111) , 1993 .

[22]  Tosatti,et al.  Vibrational spectra of atomic H and D on Cu(110): Evidence for H quantum delocalization. , 1992, Physical review letters.

[23]  D. Hamann,et al.  Theory of H bonding and vibration on Pt(111) , 1987 .

[24]  R. Nieminen,et al.  Hydrogen chemisorbed on nickel surfaces: A wave-mechanical treatment of proton motion , 1985 .