Abstract
This report summarizes our work on UV-laser induced desorption of small molecules and atoms from transition metal oxides. The systems presented serve as examples for a simple photochemical reaction, the fission of the molecule surface bond. State resolved detection methods were used to record the final state distributions of the desorbing neutral molecules. Detailed results on the systems NO/NiO(1 1 1) and CO/Cr2O3 (0 0 0 1) are presented. The experiments include investigations on stereodynamic aspects like the angular distributions of the desorbing molecules and, in the case of CO desorption, the rotational alignment with respect to the surface normal. Large desorption cross sections of (6 ± 1) · 10−17 cm2 for NO and (3.5 ± 1) · 10−17 cm2 for CO have been found for the desorption at 6.4 eV. The wavelength dependence indicates that the primary excitation step is substrate induced. The final state distributions show a high degree of translational, rotational and vibrational excitation and are clearly nonthermal of origin. The results are consistent with the formation of a negative ion intermediate state of the adsorbate. This observation is supported from a comparison to former results on NO/NiO(1 0 0) for which extensive ab initio calculations including electronically excited states exist. A spin state dependence of the vibrational excitation of NO could only be observed for NO/NiO(1 1 1) and is absent for NO/NiO(1 0 0). We attribute this observation to a spin state dependent coupling of the desorbing molecule to the surface in case the spin lattice orientation of the surface shows a preferential orientation. In the (111) plane the spin orientation is parallel within neighbour nickel ions while it is alternating in the (1 0 0) plane. For both systems studied the velocity component parallel to the surface is constant leading to a strong peaking along the surface normal for the fast molecules. The change from a preferred helicopter rotation (angular momentum vector aligned parallel to the surface normal) to a cartwheel motion (angular momentum vector aligned perpendicular to the surface normal) with increasing rotational excitation for desorption of the flat lying CO is consistent with a change of bonding geometry during the desorption process.
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References
J.C. Polanyi: Angew. Chem.99, 981 (1987)
E.B. Bourdon, P. Das, I. Harrison, J.C. Polanyi, J. Segner, C.D. Stanners, R.J. Williams, P.A. Young:Faraday Discuss. Chem. Soc. 82, 343 (1986)
J.D. Bernal:The Physical Basis of Life (Routledge and Kegan Paul, London 1951)
S.W. Fox inThe Origins of Prebiological Systems, ed. S.W. Fox(Academic Press, New York, 1965)
N. Lahav, S. Chang: J. Mol. Evolution8, 357 (1976)
D.E. Ramaker: Chem. Phys.80, 183 (1983)
J.O. Noell, C.F. Melius, R.H. Stulen: Surf. Sci.157, 119 (1985)
D.J. Ehrlich, J.Y. Tsao (eds.):Laser Microfabrication: Thin Film Processes and Lithography (Academic Press, Boston, 1989)
W. Ho: Surf. Sci.299/300, 996 (1994)
H.-L. Dai, W. Ho (eds):Laser Spectroscopy and Photochemistry n Metal Surfaces, Adv. Set. Phys. Chem.5(World Scientific, Singapore, 1995)
X.-L. Zhou, X.-Y. Zhu and J.M. White: Surface Sci. Rep.13, 73 (1991)
R.R. Cavanagh, D.S. King, J.C. Stephenson, T.F. Heinz: J. Phys. Chem.97, 786 (1993)
R.E. Palmer: Surf. Sci.307-309, 335 (1994)
M. Szymonski and Z. Postawa (eds.):Desorption induced by electronic transitions, DIET VI, Nuc. Instr. Meth. Phys. Res., Section B: Beam Interaction with Materials and Atoms101 (1995)
F.M. Zimmermann, W. Ho: Surf. Sci. Rep.22, 127 (1995)
K. Al-Shamery, H.-J. Freund: Current Opinion Sol. State Mat. Sci. vol.1/5, in press
J. Bokor: Science246, 1130 (1989)
R. Haight: Surf. Sci. Rep.21, 275 (1995)
S. Ogawa, H. Petek:Procd. of the SPIE'S OE/Laser '95 Conference,2547, 73 (1995)
E. Knoesel, T. Hertel, M. Wolf, G. Ertl: Chem. Phys. Lett.240, 409 (1995)
M. Menges, B. Baumeister, K. Al-Shamery, B. Adam, Th. Mull, H.-J. Freund, C. Fischer, D. Weide, P. Andresen inDesorption induced by electronic transitions, DIET V, eds. A.R. Burns, E.B. Stechel, D.R. Jennison: Springer Ser. Surf. Sci.31, 275 (Springer, Berlin, 1993)
M. Menges, B. Baumeister, K. Al-Shamery, H.-J. Freund, C. Fischer, P. Andresen: J. Chem. Phys.101, 3318 (1994)
M. Menges, B. Baumeister, K. Al-Shamery, H.-J. Freund, C. Fischer, P. Andresen: Surf. Sci.316, 103 (1994)
M. Wilde, K. Al-Shamery, H.-J. Freund: paper in preparation
K. Al-Shamery, I. Beauport; H.-J. Freund, H. Zacharias: Chem. Phys. Lett.222, 107 (1994)
I. Beauport, K. Al-Shamery: Proceedings of the SPIE'S OE/LASER '95 conference2547, 176 (1995)
I. Beauport, K. Al-Shamery, H.-J. Freund: Surf. Sci.363 (1996)
I. Beauport, K. Al-Shamery, H.-J. Freund: Chem. Phys. Lett.256, 641 (1996)
M. Wilde, I. Beauport, K. Al-Shamery, F. Stuhl, H.-J. Freund: paper in preparation
M.A. Fox, M.T. Dulay: Chem. Rev.93, 341 (1993)
A. Linsebigler, G. Lu, J.T. Yates: J. Phys. Chem.100, 6631 (1996)
V.P. Holbert, S.J. Garrett, P.C. Stair, E. Weitz: Surf. Sci.346, 189 (1996)
S.J. Garrett, V.P. Holbert, P.C. Stair, E. Weitz: J. Chem. Phys.100, 4615 (1994)
S.J. Garrett, V.P. Holbert, P.C. Stair, E. Weitz: J. Chem. Phys.100, 4626 (1994)
K. Domen, T.J. ChuangL: J. Chem. Phys.90, 3318 (1989)
M. Asscher, F.M. Zimmermann, L.L. Springsteen, P.L. Houston, W. Ho: J. Chem. Phys.96, 4808 (1991)
D. Weide, P. Andresen, H.-J. Freund: Chem. Phys. Lett.136, 106 (1987)
F. Budde, A.V. Hamza, P.M. Ferm, G. Ertl, D. Weide, P. Andresen, H.-J. Freund: Phys. Rev. Lett.60, 1518 (1988)
Th. Mull, M. Menges, B. Baumeister, G. Odöfer, H. Geisler, G. Illing, R.M. Jaeger, H. Kuhlenbeck, H.-J. Freund, D. Weide, U. Schüller, P. Andresen, F. Budde, P. Ferm, V. Hamza, G. Ertl: Physica Scripta41, 134 (1990)
Th. Mull, B. Baumeister, M. Menges, H.-J. Freund, D. Weide, C. Fischer, P. Andresen: J. Chem. Phys.96, 7108 (1992)
Th. Mull, H. Kuhlenbeck, G. Odöfer, R.M. Jaeger, C. Xu, B. Baumeister, M. Menges, G. Illing, H.-J. Freund, D. Weide, P. Andresen: inDesorption induced by electronic transitions, DIET IV, eds. G. Betz und P. Varga: Springer Ser. Surf. Sci.19, 143 (Springer, Heidelberg 1993)
G. Eichhorn, M. Richter, K. Al-Shamery, H. Zacharias: to be published
B. Baumeister, H.-J. Freund: J. Phys. Chem.98, 11962 (1994)
Th. Klüner, H.-J. Freund, J. Freitag, V. Staemmler: J. Chem. Phys.104, 10030 (1996)
Th. Klüner, H.-J. Freund, J. Freitag, V. Staemmler: Conference Proceedings CAT 1996, to be published in J. Mol. Catalysis, paper submitted
H. Kuhlenbeck; G. Odöfer, R. Jaeger, G. Illing, M. Menges, Th. Mull, H.-J. Freund, M. Pöhlchen, V. Staemmler, S. Witzel, C. Scharfschwerdt, K. Wennemann, T. Liedtke, M. Neumann: Phys. Rev.B43, 1969 (1991)
M. Bäumer, D. Cappus, G. Illing, H. Kuhlenbeck, H.-J. Freund: J. Vac. Sci. Technol.A10 2407 (1991)
V. Staemmler inAdsorption. on Ordered Surfaces of Ionic Solids and Thin Films, eds. H.-J. Freund, E. Umbach: Springer Ser. Surf. Sci.33 (Springer, Berlin, 1993)
M. Pöhlchen, V. Staemmler, J. Wasilewski: paper in preparation
D. Cappus, C. Xu, D. Ehrlich, B. Dillmann, C.A. Ventrice Jr., K. Al-Shamery, H. Kuhlenbeck, H.-J. Freund: Chem. Phys.117, 533 (1993)
F. Rohr, K. Wirth, J. Libuda, D. Cappus, M. Bäumer, H.-J. Freund: Surf. Sci. Lett.315, 2977 (1994)
D. Cappus, M. Haßel, E. Neuhaus, F. Rohr, H.-J. Freund: Surf. Sci.337, 268 (1995)
C. Xu, M. Hassel, H. Kuhlenbeck, H.-J. Freund: Surf Sci.258, 23 (1991)
C. Xu, B. Dillmann, H. Kuhlenbeck, H.-J. Freund: Phys. Rev. Lett.67, 3551 (1991)
H. Kuhlenbeck, C. Xu, B. Dillmann, M. Haßel, B. Adam, D. Ehrlich, S. Wohlrab, H.-J. Freund, U.A. Ditzinger, H. Neddermeyer, M. Neuber, M. Neumann: Ber. Bunsenges. Phys. Chem.96, 15 (1992)
H.-J. Freund, E. Umbach (eds.):Adsorption on Ordered Surfaces of Ionic Solids and Thin Films, Springer Ser. Surf. Sci.33 (Springer, Berlin, 1993)
D.C. Jacobs, R.N. Zare: J. Chem. Phys.85, 5457 (1986)
D.C. Jacobs, R.J. Madix, R.N. Zare: J. Chem. Phys.85, 5469 (1986)
H. Rottke, H. Zacharias: Opt. Comm.55, 87 (1985)
M. Schönnenbeck, D. Cappus, J. Klinkmann, H.-J. Freund, L.G.M. Pettersson, P.S. Bagus: Surf. Sci. Spectra, submitted
F. Winkelmann, S. Wohlrab, J. Libuda, M. Bäumer, D. Cappus, M. Menges, K. Al-Shamery, H. Kuhlenbeck, H.-J. Freund: Surf. Sci.307-309, 1148 (1994)
J. Yoshinobu, X. Guo, J.T. Yates: J. Vac. Sci. Technol.A9, 1726 (1991)
J. Yoshinobu, X. Guo, J.T. Yates: J. Chem. Phys.92, 7700 (1991)
D. Adler, J. Feinleib: Phys. Rev.B2, 3112 (1970)
A. Freitag, V. Staemmler, D. Cappus, C.A. Ventrice Jr., K. Al-Shamery, H. Kuhlenbeck, H.-J. Freund: Chem. Phys. Lett.210 10 (1993)
S. Hüfner, P. Steiner, I. Sander, M. Neumann, S. Witzel: Z. Phys. B83, 185 (1991)
P. Kuiper, G. Kruizinga, J. Ghijsen, G.A. Sawatzky, H. Verweij: Phys. Rev. Lett.62, 221 (1988)
O. Tjernberg, S. Söderholm, U.O. Karlsson, M. Qvarford, G. Chiaia, H. Nylon, I. Lindau: MAX-Lab, Activity Report, 100 (1993)
R.J. Powell, W.E. Spicer: Phys. Rev.B2, 2182 (1970)
P. Feulner, D. Menzel: inLaser Spectroscopy and Photochemistry on Metal Surfaces, edited by H.-L. Dai, W. Ho, Adv. Ser. Phys. Chem.5, 627 (World Scientific, Singapore, 1995)
C.F. Klingshirn:Semiconductor Optics. (Springer, Berlin 1995)
S.M. Harris, S. Holloway, G.R. Darling: J. Chem. Phys.102, 8235 (1995)
Gadzuk: inLaser Spectroscopy and Photochemistry on Metal Surfaces, edited by H.-L. Dai, W. Ho, Adv. Ser. Phys. Chem.5, 897 (World Scientific, Singapore, 1995)
D. Burgess Jr., R.R. Cavanagh, D.S. King: J. Chem. Phys.88, 6556 (1988)
S.A. Buntin, L.J. Richter, D.S. King, R.R. Cavanagh: J. Chem. Phys.91, 6429 (1989)
A. Peremans, K. Fukutani, K. Mase, Y. Murata: Surf. Sci.283, 189 (1993)
R.C. Jackson, J.C. Polanyi, P. Sjövall: J. Chem. Phys.102, 6308 (1995)
E. Hasselbrink, S. Jakubith, S. Nettesheim, M. Wolf, A. Cassuto, G. Ertl: J. Chem. Phys.92, 3154 (1990)
E. Hasselbrink: Chem. Phys. Lett.170, 329 (1990)
F.M. Zimmermann, W. Ho: J. Chem. Phys.101, (1994)
Y. Murata, K. Fukutani: J. Mol. Structure352/353, 519 (1995)
S.A. Buntin, L.J. Richter, R.R. Cavanagh, D.S. King: Phys. Rev. Lett.61, 1321 (1988)
A. de Meijere, H. Hirayama, E. Hasselbrink: Phys. Rev. Lett.70, 1147 (1993)
I. Harrison, V.A. Ukraintsev, A.N. Artsykhovich, SPIE Proceedings2125 (1994)
T. Hertel, M. Wolf, G. Ertl: J. Chem. Phys.102, 3414 (1995)
P.R. Antoniewicza: Phys. Rev. B21, 3811 (1980)
G. Herzberg:Molecular Spectra and Molecular Structure: Spectra of Diatomic Molecules (Van Nostrand Reinhold Company, New York, 1950)
P.A. Cox:Transition Metal Oxides: An Introduction to Their Electronic Structure and Properties (Int. Ser. Monographs on Chemistry, Oxford University Press, New York, 1995)
D. Ehrlich, Ph.D. thesis, Bochum 1995
C.H. Greene, R.N. Zare: J. Chem. Phys.78, 6741 (1983)
P.L. Houston: J. Phys. Chem.91, 5388 (1987)
R.N. Zare:Angular Momentum: Understanding spatial Aspects in Chemistry and Physics (Wiley Interscience, New York, 1988)
D.C. Jacobs, K.W. Kolasinski, S.F. Shane, R.N. Zare: J. Chem. Phys.91, 3182 (1989)
M. Bender, D. Ehrlich, I.N. Yakovkin, F. Rohr, M. Bäumer, H. Kuhlenbeck, H.-J. Freund, V. Staemmler: J. Phys: Condens. Matter7, 1 (1995)
F.M. Zimmermann, P.L. Houston, W. Ho: paper submitted
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Al-Shamery, K. Dynamics of photoinduced reactions at oxide surfaces. Appl. Phys. A 63, 509–521 (1996). https://doi.org/10.1007/BF01567207
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DOI: https://doi.org/10.1007/BF01567207