title: Experimental and theoretical study of CO collisions with CH3- and CF3-terminated self-assembled monolayers.
abstract: We present an experimental and theoretical study of the dynamics of collisions of the CO molecule with organic surfaces. Experimentally, we scatter CO at 60 kJ mol(-1) and 30 degrees incident angle from regular (CH(3)-terminated) and omega-fluorinated (CF(3)-terminated) alkanethiol self-assembled monolayers (SAMs) and measure the time-of-flight distributions at the specular angle after collision. At a theoretical level, we carry out classical-trajectory simulations of the same scattering process using CO/SAM potential-energy surfaces derived from ab initio calculations. Agreement between measured and calculated final translational energy distributions justifies use of the calculations to examine dynamical behavior of the gas/surface system not available directly from the experiment. Calculated state-to-state energy-transfer properties indicate that the collisions are notably vibrationally adiabatic. Similarly, translational energy transfer from and to CO rotation is relatively weak. These trends are examined as a function of collision energy and incident angle to provide a deeper understanding of the factors governing state-to-state energy transfer in gas/organic-surface collisions.
authors.affiliation: Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061-0212, USA.
authors.forename: William A
authors.initials: WA
authors.lastname: Alexander
authors.forename: John R
authors.initials: JR
authors.lastname: Morris
authors.forename: Diego
authors.initials: D
authors.lastname: Troya