Nonclassical behavior of energy transfer from molecules to metal surfaces: Biacetyl(3nπ*)/Ag(111)

The distance dependent lifetime of biacetyl separated from a Ag(111) crystal by NH3 spacer layers ranging in thickness from 28 to 457 A has been measured. We extended previous work, where the molecular emission was resonant with the silver interband/plasmon transition, to the case where the emission is below the interband transition. The modulation of the radiative rate is described inadequately by the classical theory for our experimental geometry. At short distances where nonradiative energy transfer to the metal is important, the classical prediction deviates from the data as well. These observations are consistent with a model in which energy is transferred to electrons localized at the metal surface but might also be explained by an inability of the classical theory to model the radiative rate properly.

[1]  B. Persson,et al.  Dynamical processes at surfaces: Excitation of electron-hole pairs , 1984 .

[2]  B. Persson,et al.  Excited states at metal surfaces and their non-radiative relaxation , 1984 .

[3]  B. Persson,et al.  On the nature and decay of electronically excited states at metal surfaces , 1983 .

[4]  P. Avouris,et al.  Nonradiative relaxation of electronically excited N2 on Al(111). Comparison with nonlocal optical theory , 1983 .

[5]  B. Persson,et al.  Electron-hole-pair quenching of excited states near a metal , 1982 .

[6]  M. Moskovits.  Surface selection rules , 1982 .

[7]  Charles B. Harris,et al.  Mechanisms for electronic energy transfer between molecules and metal surfaces: A comparison of silver and nickel , 1982 .

[8]  P. K. Aravind,et al.  The fluorescence lifetime of a molecule emitting near a surface with small, random roughness , 1982 .

[9]  L. Brus,et al.  Time resolved energy transfer from electronically excited 3B3u pyrazine molecules to planar Ag and Au surfaces , 1982 .

[10]  G. W. Ford,et al.  Electromagnetic effects on a molecule at a metal surface , 1981 .

[11]  Electrodynamics at a metal surface with applications to the spectroscopy of adsorbed molecules. I. General theory , 1980 .

[12]  P. K. Aravind,et al.  The enhancement of raman and fluorescent intensity by small surface roughness. changes in dipole emission , 1980 .

[13]  C. Harris,et al.  Electronic energy transfer to metal surfaces: a test of classical image dipole theory at short distances , 1980 .

[14]  J. Yardley,et al.  Radiationless decay from triplet state biacetyl molecules with selected vibrational energies , 1974 .

[15]  M. Scully,et al.  The Quantum Theory of Light , 1974 .

[16]  R. W. Christy,et al.  Optical Constants of the Noble Metals , 1972 .

[17]  Hans Kuhn,et al.  Classical Aspects of Energy Transfer in Molecular Systems , 1970 .

[18]  H. Morawitz.  Self-Coupling of a Two-Level System by a Mirror , 1969 .

[19]  David P. Shoemaker,et al.  Experiments in physical chemistry , 1962 .

[20]  A. Sommerfeld.  Partial Differential Equations in Physics , 1949 .