Thermal desorption of large molecules from solid surfaces.
We use molecular-dynamics simulations and importance sampling to obtain transition-state-theory rate constants for thermal desorption of an n-alkane series from Au(111). We find that the binding of a large molecule to a solid surface involves different types of local minima. The preexponential factors increase with increasing chain length and can be substantially larger than typical estimates for small molecules. Our results match recent experimental studies and indicate that a proper treatment of conformational isomerism and entropy, heretofore not found in coarse-grained models, is essential to quantitatively describe the thermal desorption of large molecules from solid surfaces.
Fichthorn
Kristen A
KA
Departments of Chemical Engineering and Physics, The Pennsylvania State University, University Park, Pennsylvania 16802, USA.
Miron
Radu A
RA