Charge-transfer photodissociation of adsorbed molecules via electron image states.

The 248 and 193 nm photodissociations of submonolayer quantities of CH(3)Br and CH(3)I adsorbed on thin layers of n-hexane indicate that the dissociation is caused by dissociative electron attachment from subvacuum level photoelectrons created in the copper substrate. The characteristics of this photodissociation-translation energy distributions and coverage dependences show that the dissociation is mediated by an image potential state which temporarily traps the photoelectrons near the n-hexane-vacuum interface, and then the charge transfers from this image state to the affinity level of a coadsorbed halomethane which then dissociates.

[1]  L. Sanche,et al.  Electron transfer reactions for image and image-derived states in dielectric thin films. , 2008, The Journal of chemical physics.

[2]  E. Jensen.  Control of photodissociation pathway for oriented adsorbed molecules using polarized light , 2006 .

[3]  E. Jensen.  Near-UV photodissociation of oriented CH3I adsorbed on Cu(110)-I. , 2005, The Journal of chemical physics.

[4]  B. V. Andryushechkin,et al.  Atomic structure of chemisorbed iodine layer on Cu(110) , 2005 .

[5]  W. Berthold,et al.  Time-resolved two-photon photoemission of buried interface states in Ar/Cu(100). , 2005, Physical review letters.

[6]  P. Feulner,et al.  Influence of Ar, Kr, and Xe layers on the energies and lifetimes of image-potential states on Cu(100) , 2004 .

[7]  C. C. Johnson,et al.  Photolysis of CH3I on Cu(110) at 337 nm: Direct and charge-transfer photodissociation , 2000 .

[8]  G. Gallup,et al.  Comparative studies of dissociative electron attachment to methyl halides , 1999 .

[9]  I. Fabrikant,et al.  Vibrational resonance and threshold effects in inelastic electron collisions with methyl iodide molecules , 1999 .

[10]  G. Ertl,et al.  Femtosecond electron dynamics at adsorbate–metal interfaces and the dielectric continuum model , 1999 .

[11]  G. Ertl,et al.  Can we control lifetimes of electronic states at surfaces by adsorbate resonances , 1998 .

[12]  I. Fabrikant,et al.  Absolute cross sections for dissociative electron attachment to condensed CH3Cl and CH3Br: Effects of potential energy curve crossing and capture probability , 1997 .

[13]  R. Lingle,et al.  Femtosecond dynamics of electrons on surfaces and at interfaces. , 1997, Annual review of physical chemistry.

[14]  Nien-Hui Ge,et al.  Femtosecond studies of electron tunneling at metal-dielectric interfaces , 1996 .

[15]  Bass,et al.  Effect of the Condensed Phase on Dissociative Electron Attachment: CH3Cl Condensed on a Kr Surface. , 1995, Physical review letters.

[16]  Rous.  Negative ion formation in adsorbed molecules: The role of surface states. , 1995, Physical review letters.

[17]  F. Weik,et al.  Wavelength dependence of the photochemistry of O2 on Pd(111) and the role of hot electron cascades , 1993 .

[18]  J. Polanyi,et al.  Photochemistry of adsorbed molecules. XII: Photoinduced ion-molecule reactions at a metal surface for CH3X/RCl/Ag(111) (X=Br, I) , 1993 .

[19]  I. Harrison,et al.  Photofragmentation dynamics of submonolayers of CH3Br adsorbed on Pt(111) , 1992 .

[20]  K. Ertl,et al.  Adsorbate-induced enhancement of image-potential surface states on Ni(110) , 1992 .

[21]  X.-L. Zhou,et al.  Photochemistry at adsorbate/metal interfaces , 1991 .

[22]  L. Sanche,et al.  The 2Πg shape resonance of N2 near a metal surface and in rare gas solids , 1990 .

[23]  A. E. Vries,et al.  Photofragmentation of CH3Br in the A band , 1985 .

[24]  C. C. Grimes,et al.  Direct Spectroscopic Observation of Electrons in Image-Potential States Outside Liquid Helium , 1974 .

[25]  R. C. Weast.  CRC Handbook of Chemistry and Physics , 1973 .

[26]  M. W. Cole,et al.  Image-potential-induced surface bands in insulators , 1969 .