How adiabatic is activated adsorption/associative desorption?

• Published in: The Journal of chemical physics Vol. 123; no. 7; p. 074704
• Main Authors: Luntz, A C, Persson, M
• Format: Journal Article
• Language: English
• Published: United States 15.08.2005
• ISSN: 0021-9606
• DOI: 10.1063/1.2000249

Using density-functional theory we calculate friction coefficients describing the damping of nuclear motion into electron-hole pair excitation for the two best-known examples of activated adsorption: H2 dissociation on a Cu(111) surface and N2 dissociation on a Ru(0001) surface. In both cases, the frictions increase dramatically along the reaction path towards the transition state and can be an order of magnitude larger there than typical in the molecularly adsorbed state. In addition, the frictions for N2/Ru(0001) are typically an order of magnitude larger than for H2/Cu(111). We rationalize these trends in terms of the electron structure as the systems proceed to dissociation along the reaction paths. Combining these friction coefficients with the potential-energy surface in quasiclassical dynamics allows first-principles studies of the importance of the breakdown in the Born-Oppenheimer approximation in describing the chemistry. We find that nonadiabatic effects are minimal for the H2/Cu(111) system, but are quite important for N2/Ru(0001).