Cross sections and NO product state distributions resulting from substrate mediated photodissociation of NO2 adsorbed on Pd(111)
J. Chem. Phys. 92, 3154 (1990); doi:10.1063/1.457913
Issue Date: 1 March 1990
You are logged in to this journal.
Ultraviolet irradiation of NO2 adsorbed on top of a NO saturated Pd(111) surface causes the photodissociation of NO2/N2O4 and results in the desorption of NO molecules. This process has been studied using excitation energies between 3.5 and 6.4 eV. At a photon energy of 6.4 eV, a cross section of 3×10−18 cm2 is found. Using laser-induced fluorescence to detect the desorbed NO molecules, fully state-resolved data detailing the energy channeling into different degrees of freedom has been obtained. Two desorption channels are found, one characterized by nonthermal state populations, and one showing accommodation to the surface. The yield of the fast channel shows a marked increase above 4 eV photon energy. The slow channel is interpreted as being due to NO molecules which, after formation, undergo a trapping–desorption process. A polarization experiment indicates that the photodissociation is initiated by excitation of metal electrons rather than direct absorption by the adsorbate.
The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
| History: | Received 2 August 1989; accepted 14 November 1989 |
| Permalink: |
http://link.aip.org/link/?JCPSA6/92/3154/1 |
KEYWORDS and PACS
PHOTODISSOCIATION,
ADSORBATES,
NITROGEN DIOXIDE,
DESORPTION,
PALLADIUM,
SORPTIVE PROPERTIES,
NITRIC OXIDE,
CHEMICAL REACTION YIELD,
ENERGY&minus,
LEVEL DENSITY
- 82.50.Fv
Physical chemistry Photochemistry and radiation chemistry Photolysis, photodissociation, and photoionization by infrared, visible, and ultraviolet radiation - 82.65.My
Physical chemistry Surface and interface chemistry Chemisorption - 82.20.Rp
Physical chemistry Chemical kinetics Energy distribution and transfer; relaxation - YEAR: 1990
PUBLICATION DATA
0021-9606 (print)
1089-7690 (online)
REFERENCES (54)
-
T. J. Chuang, Surf. Sci. Rep. 3, 1 (1983). [Inspec] [ChemPort]
-
S. R. Leone, Adv. Chem. Phys. 50, 255 (1982); [ChemPort]
-
P. Avouris and R. E. Walkup, Annu. Rev. Phys. Chem. 40, 173 (1989). [ISI] [ChemPort]
-
Z. Ying and W. Ho, Phys. Rev. Lett. 60, 57 (1988); [ISI] [MEDLINE] [ChemPort]
-
E. B. D. Bourdon, J. P. Cowin, I. Harrison, J. C. Polanyi, J. Segner, C. D. Stanners, and P. A. Young, J. Phys. Chem. 88, 6100 (1984); [Inspec] [ISI] [ChemPort]
-
F. L. Tabares, E. P. Marsh, G. A. Bach, and J. P. Cowin, J. Chem. Phys. 86, 738 (1987). [ISI] [ChemPort]
-
E. P. Marsh, M. R. Schneider, T. L. Gilton, F. L. Tabares, W. Meier, and J. P. Cowin, Phys. Rev. Lett. 60, 2551 (1988). [ISI] [MEDLINE] [ChemPort]
-
E. P. Marsh, T. L. Gilton, W. Meier, M. R. Schneider, and J. P. Cowin, Phys. Rev. Lett. 61, 2725 (1988). [ISI] [MEDLINE] [ChemPort]
-
S. A. Costello, B. Roop, Z. M. Liu, and J. M. White, J. Phys. Chem. 92, 1019 (1988); [ChemPort]
-
F. Budde, A. V. Hamza, P. M. Ferm, G. Ertl, D. Weide, P. Andresen, and H.-J. Freund, Phys. Rev. Lett. 60, 1518 (1988); [ISI] [MEDLINE] [ChemPort]
-
S. A. Buntin, L. J. Richter, R. R. Cavanagh, and D. S. King, Phys. Rev. Lett. 61, 1321 (1988); [ISI] [MEDLINE] [ChemPort]
-
W. C. Natzle, D. Padowitz, and S. J. Sibener, J. Chem. Phys. 88, 7975 (1988). [ISI] [ChemPort]
-
A. M. Bass, A. E. L. Ledford, Jr., and A. H. Laufer, J. Res. Natl. Bur. Stand. Sect. A 80, 143 (1976). [Inspec]
-
C. H. Chen, D. W. Clark, M. G. Payne, and S. D. Kramer, Opt. Commun. 32, 391 (1980). [Inspec]
-
H. Zacharias, M. Geilhaupt, K. Meier, and K. H. Welge, J. Chem. Phys. 74, 218 (1981); [ISI] [ChemPort]
-
T. G. Slanger, W. K. Bischel, and M. J. Dyer, J. Chem. Phys. 79, 2231 (1983). [ISI]
-
R. J. S. Morrison and E. R. Grant, J. Chem. Phys. 77, 5994 (1982); [ISI] [ChemPort]
-
M.-R. Taherian, P. C. Cosby, and T. G. Slanger, J. Phys. Chem. 91, 2304 (1987). [ChemPort]
-
M. Kawasaki, K. Kasatani, H. Sato, H. Shinohara, and N. Nishi, Chem. Phys. 78, 65 (1983). [Inspec] [ISI] [ChemPort]
-
K. Domen and T. J. Chuang, Phys. Rev. Lett. 59, 1484 (1987). [ISI] [MEDLINE]
-
A. Mödl, H. Robota, J. Segner, W. Vielhaber, M. C. Lin, and G. Ertl, J. Chem. Phys. 83, 4800 (1985). [ISI]
-
H. Conrad, G. Ertl, J. Küppers, and E. E. Latta, Surf. Sci. 65, 235 (1977). [Inspec] [ISI] [ChemPort]
-
D. Burgess, Jr., P. C. Stair, and E. Weitz, J. Vac. Sci. Technol. A 4, 1362 (1986). [ISI] [ChemPort]
-
Physik Daten, edited by H. Behrens and G. Ebel (Fachinformationszentrum, Karlsruhe, 1981), Vol. 18-1.
-
This assumption has been made based on the voltages presented in the QMS. More accurate time-of-flight data is obtained using laser detection, where the time relation is better denned. The integral data has been compared to this measurement indicating a slightly higher flight time (~20 µs) through the QMS.
-
M. S. Chou, A. M. Dean, and D. Stern, J. Chem. Phys. 78, 5962 (1983). [ISI]
-
F. Budde, T. Gritsch, A. Mödl, T. J. Chuang, and G. Ertl, Surf. Sci. 178, 798 (1986). [Inspec] [ISI] [ChemPort]
-
H.-D. Schmick and H.-W. Wassmuth, Surf. Sci. 123, 471 (1982). [Inspec] [ISI] [ChemPort]
-
M. Bertolo and K. Jacobi, Surf. Sci. (in press);
-
This data has been obtained using the mass spectrometer tuned on mass 30 (NO). NO2 is detected on this e/m setting with a rel. probability of 60%.
-
M. E. Bartram, R. G. Windham, and B. E. Koel, Surf. Sci. 184, 57 (1987). [Inspec] [ChemPort]
-
This choice has been made because the structure of the physisorbed NO2 layer is unknown. Some care has to be taken in order to avoid misleading results due the different pumping speeds observed for NO and NO2. But at higher heating rates this effect becomes negligible. From the bulk density of N2O4 with 1.5 g/cm3 it is estimated that 0.5 ML are equivalent to one completed layer of NO2.
-
Landolt-Börnstein Band II, 4 Teil (Springer, Berlin, 1961).
-
H.-J. Freund and M. Neumann, Appl. Phys. A 47, 3 (1988). [Inspec]
-
G. A. Bootsma and F. Meyer, Surf. Sci. 14, 52 (1969). [Inspec] [ISI] [ChemPort]
-
J. D. E. McIntyre, Adv. Electrochem. Electrochem. Eng. 9, 68 (1973).
-
We used as optical constants the following values: 5.0 eV; n = 0.96 and k = 1.86; 6.4 eV; n = 0.73 and k = 1.29, from Ref. 24.
-
Gmelin, Bd. 4 (Verlag, Chemie, Berlin, 1936).
-
U. Schwalke, J. E. Parmeter, and W. H. Weinberg, J. Chem. Phys. 84, 4036 (1986). [ISI] [ChemPort]
-
B. W. McClelland, G. Gundersen, and K. Hedberg, J. Chem. Phys. 56, 4541 (1972). [ISI] [ChemPort]
-
J. E. Demuth, Chem. Phys. Lett. 45, 12 (1977). [Inspec] [ISI]
-
L. G. Christophorou, D. L. McCorkle, and A. A. Christodoulides, in Electron-Molecule Interactions and Their Application, edited by L. G. Christophorou (Academic, Orlando, FL, 1984), Vol. 1, pp. 478–617.
-
D. Menzel, Nucl. Instrum. Methods B 13, 507 (1986); [Inspec] [ISI]
-
F. Bolduan, H. J. Jodl, and A. Loewenschuss, J. Chem. Phys. 80, 1739 (1984). [ChemPort]
-
K. M. Erwin, J. Ho, and W. C. Lineberger, J. Phys. Chem. 92, 5405 (1988). [ISI] [ChemPort]
-
The heat of formation of NO
is referenced as −3.49 eV in: S. J. Ashcroft and G. Beech, Inorganic Chemistry (VanNostrand, London, 1973), p. 20.
-
Assuming a frequency factor of 1013 s−1 a residence time of 8 ns is calculated.
-
A. L. Harris, J. K. Brown, and C. B. Harris, Annu. Rev. Phys. Chem. 39, 341 (1988). [ISI] [ChemPort]
-
M. Wolf, A. Cassuto, S. Nettesheim, E. Hasselbrink, and G. Ertl (to be published).
-
A. Mödi, H. Robota, J. Segner, W. Vielhaber, M. C. Lin, and G. Ertl, Surf. Sci. 169, L341 (1986). [ISI]
-
R. Schinke, Annu. Rev. Phys. Chem. 39, 39 (1988). [ISI] [ChemPort]
-
R. Gomer, in Desorption Induced by Electronic Transition, DIET I, edited by N. H. Tolk, M. M. Traum, J. C. Tully, and T. E. Madey, Springer Series in Chemical Physics (Springer, Berlin, 1983), Vol. 24, p. 40.
-
A. R. Burns, E. B. Stechel, and D. R. Jennison, Phys. Rev. Lett. 58, 250 (1987); [ISI] [MEDLINE] [ChemPort]
-
E. Hasselbrink (to be published).
Advances in Gas-Phase Photochemistry and Kinetics, Molecular Photodissociation Dynamics, edited by N. M. R. Ashfold and J. E. Baggot (Royal Society of Chemistry, London, 1987).
I. Harrison, J. C. Polanyi, and P. A. Young, J. Chem. Phys. 89, 1475 (1988). [ISI] [ChemPort]
B. Roop, K. G. Lloyd, S. A. Costello, A. Campion, and J. M. White, J. Chem. Phys. 91, 5103 (1989); [ChemPort]
X.-Y. Zhu, S. R. Hatch, A. Campion, and J. M. White, ibid. 91, 5011 (1989). [ISI] [ChemPort]
J. Chem. Phys. 87, 360 (1987). [ChemPort]
E. B. Stechel, D. R. Jennison, and A. R. Burns, ibid. pp. 136–143.








