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Scattering Dynamics, Survival, and Dispersal of Dimethyl Methylphosphonate Interacting with the Surface of Multilayer
1The James Franck Institute and Department of Chemistry, The University of Chicago , 929 East 57th Street, Chicago, Illinois 60637, United States.
Abstract:
We explored the interaction of a molecular beam of dimethyl methylphosphonate with a multilayer graphene surface to better understand the fate of chemical warfare agents in the environment. The experiments were done at surface temperatures between 120 and 900 K and translational energies between 200 and 1500 meV. At the lowest temperatures, the dimethyl methylphosphonate is adsorbed, with the molecules next to the carbon surface held slightly more strongly than the bulk molecular film that grows with continued dosing. We measured the desorption energy for submonolayer coverage using modulated beam techniques and found a value of 290 meV (28 kJ/mol). At higher surface temperatures, where the residence times are very short, we measured the scattering of the dimethyl methylphosphonate as a function of angle and translational kinetic energy. For a surface temperature of 250 K, with translational kinetic energies between 200 and 1500 meV, much of the incident flux has nearly been accommodated by the surface temperature and has no memory of the incident momentum. The internal energy also seems to be at least partially accommodated. As the surface temperature increases, the scattering transitions to direct-inelastic reflection, where much of the incident translational energy is retained, and the intensity of the scattering peaks superspecularly toward glancing final angles. These results demonstrate the efficacy of using kinetic energy controlled molecular beams to probe the interactions of complex organic molecules with well-defined surfaces, extending our fundamental understanding of how the dynamics for such systems crossover from trapping-desorption to direct inelastic scattering. Moreover, these results indicate that simulations that model the dispersal of chemical warfare agents using common interfaces in the environment need to account for multiple bounce trajectories and survival of the impinging molecules.
