Abstract
We use accelerated molecular dynamics to probe the thermal desorption of n-alkanes from the Au(1 1 1) and C(0 0 0 1) surfaces. Studying an alkane series ranging from CH4 to C16H34, we find that the desorption prefactor increases with increasing chain length for the short chains until a certain chain length is reached when it becomes essentially constant and independent of chain length. We can understand the dependence of the preexponential factor on alkane chain length in terms of conformational changes within the alkane molecules. For the shorter molecules, the desorption temperatures probed in experimental temperature-programmed desorption studies lie below those for which torsional motion is activated. Thus, the short alkanes can be treated as rigid rods, and the loss in translational and rotational entropy upon adsorption leads to a preexponential factor that increases with increasing chain length. As the alkane chain length increases, the binding energy and the experimental desorption temperatures also increase. Thus, torsional motion is activated to an extent that increases with increasing chain length. This torsional activation increases the entropy of adsorption and counteracts the entropy decrease due to a loss of translation and rotation. This leads to a virtually constant prefactor for sufficiently long chains. Our findings are consistent with experimental data for the thermal desorption of alkanes from the Au(1 1 1), Pt(1 1 1), MgO(1 0 0) and C(0 0 0 1) surfaces.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 71-76 |
| Number of pages | 6 |
| Journal | Catalysis Today |
| Volume | 123 |
| Issue number | 1-4 |
| DOIs | |
| State | Published - May 30 2007 |
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All Science Journal Classification (ASJC) codes
- Catalysis
- Chemistry(all)
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Molecular simulation of temperature-programmed desorption. / Fichthorn, Kristen A.; Becker, Kelly E.; Miron, Radu A.
In: Catalysis Today, Vol. 123, No. 1-4, 30.05.2007, p. 71-76.Research output: Contribution to journal › Article
TY - JOUR
T1 - Molecular simulation of temperature-programmed desorption
AU - Fichthorn, Kristen A.
AU - Becker, Kelly E.
AU - Miron, Radu A.
PY - 2007/5/30
Y1 - 2007/5/30
N2 - We use accelerated molecular dynamics to probe the thermal desorption of n-alkanes from the Au(1 1 1) and C(0 0 0 1) surfaces. Studying an alkane series ranging from CH4 to C16H34, we find that the desorption prefactor increases with increasing chain length for the short chains until a certain chain length is reached when it becomes essentially constant and independent of chain length. We can understand the dependence of the preexponential factor on alkane chain length in terms of conformational changes within the alkane molecules. For the shorter molecules, the desorption temperatures probed in experimental temperature-programmed desorption studies lie below those for which torsional motion is activated. Thus, the short alkanes can be treated as rigid rods, and the loss in translational and rotational entropy upon adsorption leads to a preexponential factor that increases with increasing chain length. As the alkane chain length increases, the binding energy and the experimental desorption temperatures also increase. Thus, torsional motion is activated to an extent that increases with increasing chain length. This torsional activation increases the entropy of adsorption and counteracts the entropy decrease due to a loss of translation and rotation. This leads to a virtually constant prefactor for sufficiently long chains. Our findings are consistent with experimental data for the thermal desorption of alkanes from the Au(1 1 1), Pt(1 1 1), MgO(1 0 0) and C(0 0 0 1) surfaces.
AB - We use accelerated molecular dynamics to probe the thermal desorption of n-alkanes from the Au(1 1 1) and C(0 0 0 1) surfaces. Studying an alkane series ranging from CH4 to C16H34, we find that the desorption prefactor increases with increasing chain length for the short chains until a certain chain length is reached when it becomes essentially constant and independent of chain length. We can understand the dependence of the preexponential factor on alkane chain length in terms of conformational changes within the alkane molecules. For the shorter molecules, the desorption temperatures probed in experimental temperature-programmed desorption studies lie below those for which torsional motion is activated. Thus, the short alkanes can be treated as rigid rods, and the loss in translational and rotational entropy upon adsorption leads to a preexponential factor that increases with increasing chain length. As the alkane chain length increases, the binding energy and the experimental desorption temperatures also increase. Thus, torsional motion is activated to an extent that increases with increasing chain length. This torsional activation increases the entropy of adsorption and counteracts the entropy decrease due to a loss of translation and rotation. This leads to a virtually constant prefactor for sufficiently long chains. Our findings are consistent with experimental data for the thermal desorption of alkanes from the Au(1 1 1), Pt(1 1 1), MgO(1 0 0) and C(0 0 0 1) surfaces.
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U2 - 10.1016/j.cattod.2006.12.003
DO - 10.1016/j.cattod.2006.12.003
M3 - Article
AN - SCOPUS:34248531418
VL - 123
SP - 71
EP - 76
JO - Catalysis Today
JF - Catalysis Today
SN - 0920-5861
IS - 1-4
ER -