Determination of toluene hydrogenation kinetics with neutron diffraction

Total neutron scattering has been used to follow the hydrogenation of toluene-d₈ to methylcyclohexane-d₁₄ over 3 wt% platinum supported on highly ordered mesoporous silica (MCM-41) at 298 K and under 150 mbar D₂ pressure. The detailed kinetic information so revealed indicates that liquid reorganisation inside pores is the slowest step of the whole process. Additionally, the results were compared with the reaction performed under 250 mbar D₂ pressure as well as with toluene-h₈ hydrogenation using D₂ at 150 mbar.

Efficient simulations with electronic open boundaries

We present a reformulation of the hairy-probe method for introducing electronic open boundaries that is appropriate for steady-state calculations involving nonorthogonal atomic basis sets. As a check on the correctness of the method we investigate a perfect atomic wire of Cu atoms and a perfect nonorthogonal chain of H atoms. For both atom chains we find that the conductance has a value of exactly one quantum unit and that this is rather insensitive to the strength of coupling of the probes to the system, provided values of the coupling are of the same order as the mean interlevel spacing of the system without probes. For the Cu atom chain we find in addition that away from the regions with probes attached, the potential in the wire is uniform, while within them it follows a predicted exponential variation with position. We then apply the method to an initial investigation of the suitability of graphene as a contact material for molecular electronics. We perform calculations on a carbon nanoribbon to determine the correct coupling strength of the probes to the graphene and obtain a conductance of about two quantum units corresponding to two bands crossing the Fermi surface. We then compute the current through a benzene molecule attached to two graphene contacts and find only a very weak current because of the disruption of the π conjugation by the covalent bond between the benzene and the graphene. In all cases we find that very strong or weak probe couplings suppress the current.