### Abstract

We use molecular-dynamics simulations and importance sampling to obtain transition-state theory rate constants for thermal desorption of an n-alkane series from Pt(111). These simulations indicate that the binding of a large molecule to a solid surface is a complex phenomenon involving many local minima. The existence of local minima invalidates the interpretation of thermal desorption as a single, first-order rate process. Because the number of local minima increases with increasing chain length, n-alkane adsorption becomes increasingly dominated by entropy for longer chains. Consequently, the binding energy increases in a less-than-linear way with increasing chain length. Our results provide a quantitative explanation for results and trends in recent experimental studies.

Original language | English (US) |
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Title of host publication | 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002 |

Editors | M. Laudon, B. Romanowicz |

Pages | 156-158 |

Number of pages | 3 |

State | Published - Dec 1 2002 |

Event | 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002 - San Juan, Puerto Rico Duration: Apr 21 2002 → Apr 25 2002 |

### Publication series

Name | 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002 |
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### Other

Other | 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002 |
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Country | Puerto Rico |

City | San Juan |

Period | 4/21/02 → 4/25/02 |

### Fingerprint

### All Science Journal Classification (ASJC) codes

- Engineering(all)

### Cite this

*2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002*(pp. 156-158). (2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002).

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*2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002.*2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002, pp. 156-158, 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002, San Juan, Puerto Rico, 4/21/02.

**Multi-scale simulation of the thermal desorption of large molecules from solid surfaces.** / Fichthorn, Kristen Ann; Miron, R. A.; Kulkarni, Anil Kamalakant.

Research output: Chapter in Book/Report/Conference proceeding › Conference contribution

TY - GEN

T1 - Multi-scale simulation of the thermal desorption of large molecules from solid surfaces

AU - Fichthorn, Kristen Ann

AU - Miron, R. A.

AU - Kulkarni, Anil Kamalakant

PY - 2002/12/1

Y1 - 2002/12/1

N2 - We use molecular-dynamics simulations and importance sampling to obtain transition-state theory rate constants for thermal desorption of an n-alkane series from Pt(111). These simulations indicate that the binding of a large molecule to a solid surface is a complex phenomenon involving many local minima. The existence of local minima invalidates the interpretation of thermal desorption as a single, first-order rate process. Because the number of local minima increases with increasing chain length, n-alkane adsorption becomes increasingly dominated by entropy for longer chains. Consequently, the binding energy increases in a less-than-linear way with increasing chain length. Our results provide a quantitative explanation for results and trends in recent experimental studies.

AB - We use molecular-dynamics simulations and importance sampling to obtain transition-state theory rate constants for thermal desorption of an n-alkane series from Pt(111). These simulations indicate that the binding of a large molecule to a solid surface is a complex phenomenon involving many local minima. The existence of local minima invalidates the interpretation of thermal desorption as a single, first-order rate process. Because the number of local minima increases with increasing chain length, n-alkane adsorption becomes increasingly dominated by entropy for longer chains. Consequently, the binding energy increases in a less-than-linear way with increasing chain length. Our results provide a quantitative explanation for results and trends in recent experimental studies.

UR - http://www.scopus.com/inward/record.url?scp=6344262054&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=6344262054&partnerID=8YFLogxK

M3 - Conference contribution

AN - SCOPUS:6344262054

SN - 0970827563

T3 - 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002

SP - 156

EP - 158

BT - 2002 International Conference on Computational Nanoscience and Nanotechnology - ICCN 2002

A2 - Laudon, M.

A2 - Romanowicz, B.

ER -