10 Surface-Aligned Femtochemistry: Dynamics on Oxide Surfaces
255
The findings presented here demonstrate the potential of the new experimental
technique of surface pump-probe fs-laser mass spectrometry to reveal the detailed
dynamics of a wide variety of bimolecular surface-aligned reactions. The unique
possibility to measure directly the surface transition state and product formation dynamics is of importance to the revelation of even complex reaction mechanisms in
surface chemistry and heterogeneous catalysis. In recent experiments the investigations were extended to reactions on metallic surfaces [122, 123] and oxide supported
metal particles [92, 124]. Furthermore, future investigations will include different
co-adsorbate molecules like O 2 , N 2 O and CO 2 in addition to the methyl halides.
In this respect it could be shown most recently that the irradiation of co-adsorption
layers of CH 3 I and CH 3 Br lead to the detection of IBr molecules. This result confirms that the observation of a reaction dynamics involving fragments from different
adsorbates is indeed feasible [68].
Acknowledgement The research presented in this contribution was supported by the Deutsche
Forschungsgemeinschaft (DFG), the Fonds der Chemischen Industrie (FCI), and by Deutscher
Akademischer Austauschdienst (DAAD).
References
1. G. Ertl, Reactions at surfaces: from atoms to complexity (Nobel lecture). Angew. Chem., Int.
Ed. Engl. 47, 3524–3535 (2008)
2. G. Ertl, Reactions at Solid Surfaces (Wiley, New York, 2009)
3. R.D. Levine, R.B. Bernstein, Molecular Reaction Dynamics (Oxford University Press, Oxford, 1988)
4. J.C. Polanyi, A.H. Zewail, Direct observation of the transition state. Acc. Chem. Res. 28,
119–132 (1995)
5. Z. Ning, J.C. Polanyi, Surface aligned reaction. J. Chem. Phys. 137, 091706 (2012)
6. S. Buelow, G. Radhakrishnan, J. Catanzarite, C. Wittig, The use of van der Waals forces to
orient chemical reactants: the H + CO 2 reaction. J. Chem. Phys. 83, 444–445 (1985)
7. S. Buelow, M. Noble, G. Radhakrishnan, H. Reisler, C. Wittig, G. Hancock, The role of
initial conditions in elementary gas-phase processes involving intermediate “complexes”.
J. Phys. Chem. 90, 1015–1027 (1986)
8. N.F. Scherer, C. Sipes, R.B. Bernstein, A.H. Zewail, Real-time clocking of bimolecular reactions: application to H + CO 2 . J. Chem. Phys. 92, 5239–5259 (1990)
9. J.C. Polanyi, H. Rieley, Photochemistry in the adsorbed state, in Dynamics of Gas-Surface
Interactions, ed. by C.T. Rettner, M.N.R. Ashfold (Royal Chem. Soc., London, 1991), p. 329
10. J.C. Polanyi, Y. Zeiri, Dynamics of adsorbate photochemistry, in Laser Spectroscopy and
Photochemistry on Metal Surfaces, ed. by H.-L. Dai, W. Ho (World Scientific, Singapore,
1995), p. 1241
11. A.H. Zewail, Femtochemistry: atomic-scale dynamics of the chemical bond. J. Phys. Chem.
A 104, 5660–5694 (2000)
12. C. Frischkorn, M. Wolf, Femtochemistry on metal surfaces: nonadiabatic reaction dynamics.
Chem. Rev. 106, 4207–4233 (2006)
13. H.-L. Dai, W. Ho (eds.), Laser Spectroscopy and Photochemistry on Metal Surfaces (World
Scientific, Singapore, 1995)
14. H. Petek, S. Ogawa, Surface femtochemistry: observation and quantum control of frustrated
desorption of alkali atoms from noble metals. Annu. Rev. Phys. Chem. 53, 507–531 (2002)
255
The findings presented here demonstrate the potential of the new experimental
technique of surface pump-probe fs-laser mass spectrometry to reveal the detailed
dynamics of a wide variety of bimolecular surface-aligned reactions. The unique
possibility to measure directly the surface transition state and product formation dynamics is of importance to the revelation of even complex reaction mechanisms in
surface chemistry and heterogeneous catalysis. In recent experiments the investigations were extended to reactions on metallic surfaces [122, 123] and oxide supported
metal particles [92, 124]. Furthermore, future investigations will include different
co-adsorbate molecules like O 2 , N 2 O and CO 2 in addition to the methyl halides.
In this respect it could be shown most recently that the irradiation of co-adsorption
layers of CH 3 I and CH 3 Br lead to the detection of IBr molecules. This result confirms that the observation of a reaction dynamics involving fragments from different
adsorbates is indeed feasible [68].
Acknowledgement The research presented in this contribution was supported by the Deutsche
Forschungsgemeinschaft (DFG), the Fonds der Chemischen Industrie (FCI), and by Deutscher
Akademischer Austauschdienst (DAAD).
References
1. G. Ertl, Reactions at surfaces: from atoms to complexity (Nobel lecture). Angew. Chem., Int.
Ed. Engl. 47, 3524–3535 (2008)
2. G. Ertl, Reactions at Solid Surfaces (Wiley, New York, 2009)
3. R.D. Levine, R.B. Bernstein, Molecular Reaction Dynamics (Oxford University Press, Oxford, 1988)
4. J.C. Polanyi, A.H. Zewail, Direct observation of the transition state. Acc. Chem. Res. 28,
119–132 (1995)
5. Z. Ning, J.C. Polanyi, Surface aligned reaction. J. Chem. Phys. 137, 091706 (2012)
6. S. Buelow, G. Radhakrishnan, J. Catanzarite, C. Wittig, The use of van der Waals forces to
orient chemical reactants: the H + CO 2 reaction. J. Chem. Phys. 83, 444–445 (1985)
7. S. Buelow, M. Noble, G. Radhakrishnan, H. Reisler, C. Wittig, G. Hancock, The role of
initial conditions in elementary gas-phase processes involving intermediate “complexes”.
J. Phys. Chem. 90, 1015–1027 (1986)
8. N.F. Scherer, C. Sipes, R.B. Bernstein, A.H. Zewail, Real-time clocking of bimolecular reactions: application to H + CO 2 . J. Chem. Phys. 92, 5239–5259 (1990)
9. J.C. Polanyi, H. Rieley, Photochemistry in the adsorbed state, in Dynamics of Gas-Surface
Interactions, ed. by C.T. Rettner, M.N.R. Ashfold (Royal Chem. Soc., London, 1991), p. 329
10. J.C. Polanyi, Y. Zeiri, Dynamics of adsorbate photochemistry, in Laser Spectroscopy and
Photochemistry on Metal Surfaces, ed. by H.-L. Dai, W. Ho (World Scientific, Singapore,
1995), p. 1241
11. A.H. Zewail, Femtochemistry: atomic-scale dynamics of the chemical bond. J. Phys. Chem.
A 104, 5660–5694 (2000)
12. C. Frischkorn, M. Wolf, Femtochemistry on metal surfaces: nonadiabatic reaction dynamics.
Chem. Rev. 106, 4207–4233 (2006)
13. H.-L. Dai, W. Ho (eds.), Laser Spectroscopy and Photochemistry on Metal Surfaces (World
Scientific, Singapore, 1995)
14. H. Petek, S. Ogawa, Surface femtochemistry: observation and quantum control of frustrated
desorption of alkali atoms from noble metals. Annu. Rev. Phys. Chem. 53, 507–531 (2002)