Nanotech 2002 Vol. 2
Nanotech 2002 Vol. 2
Technical Proceedings of the 2002 International Conference on Computational Nanoscience and Nanotechnology

Extended-Scale Atomistics Chapter 8

Multiscale Simulation of the Thermal Desorption of Large Molecules from Solid Surfaces

Authors: K. Fichthorn, R.A. Miron and A. Kulkarni

Affilation: Pennsylvania State University, United States

Pages: 156 - 158

Keywords: molecular dynamics, transition-state theory, thermal desorption

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.

ISBN: 0-9708275-6-3
Pages: 504