Details
| Original language | English |
|---|---|
| Article number | 044701 |
| Journal | Journal of Chemical Physics |
| Volume | 124 |
| Issue number | 4 |
| Publication status | Published - 23 Jan 2006 |
Abstract
The bistable CO oxidation on a nanoscale surface is characterized by a limited number of reacting molecules on the catalytic area. Internal fluctuations due to finite-size effects are studied by the master equation with a Langmuir-Hinshelwood mechanism for CO oxidation. Analytical solutions can be found in a reduced one-component model after the adiabatic elimination of one variable which in our case is the oxygen coverage. It is shown that near the critical point, with decreasing surface area, one cannot distinguish between two macroscopically stable stationary states. This is a consequence of the large fluctuations in the coverage which occur on a fast time scale. Under these conditions, the transition times between the macroscopic states also are no longer separated from the short-time scale of the coverage fluctuations as is the case for large surface areas and far away from the critical point. The corresponding stationary solutions of the probability distribution and the mean first passage times calculated in the reduced model are supported by numerics of the full two-component model.
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In: Journal of Chemical Physics, Vol. 124, No. 4, 044701, 23.01.2006.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Theoretical analysis of internal fluctuations and bistability in CO oxidation on nanoscale surfaces
AU - Pineda, M.
AU - Imbihl, R.
AU - Schimansky-Geier, L.
AU - Zülicke, Ch
PY - 2006/1/23
Y1 - 2006/1/23
N2 - The bistable CO oxidation on a nanoscale surface is characterized by a limited number of reacting molecules on the catalytic area. Internal fluctuations due to finite-size effects are studied by the master equation with a Langmuir-Hinshelwood mechanism for CO oxidation. Analytical solutions can be found in a reduced one-component model after the adiabatic elimination of one variable which in our case is the oxygen coverage. It is shown that near the critical point, with decreasing surface area, one cannot distinguish between two macroscopically stable stationary states. This is a consequence of the large fluctuations in the coverage which occur on a fast time scale. Under these conditions, the transition times between the macroscopic states also are no longer separated from the short-time scale of the coverage fluctuations as is the case for large surface areas and far away from the critical point. The corresponding stationary solutions of the probability distribution and the mean first passage times calculated in the reduced model are supported by numerics of the full two-component model.
AB - The bistable CO oxidation on a nanoscale surface is characterized by a limited number of reacting molecules on the catalytic area. Internal fluctuations due to finite-size effects are studied by the master equation with a Langmuir-Hinshelwood mechanism for CO oxidation. Analytical solutions can be found in a reduced one-component model after the adiabatic elimination of one variable which in our case is the oxygen coverage. It is shown that near the critical point, with decreasing surface area, one cannot distinguish between two macroscopically stable stationary states. This is a consequence of the large fluctuations in the coverage which occur on a fast time scale. Under these conditions, the transition times between the macroscopic states also are no longer separated from the short-time scale of the coverage fluctuations as is the case for large surface areas and far away from the critical point. The corresponding stationary solutions of the probability distribution and the mean first passage times calculated in the reduced model are supported by numerics of the full two-component model.
UR - http://www.scopus.com/inward/record.url?scp=31544451042&partnerID=8YFLogxK
U2 - 10.1063/1.2140709
DO - 10.1063/1.2140709
M3 - Article
AN - SCOPUS:31544451042
VL - 124
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
SN - 0021-9606
IS - 4
M1 - 044701
ER -