Simulation of chiral ordering process in the adsorption of chiral organic molecules on metal surfaces by Monte Carlo methods

• Main Author: Ayissi, Serge Olivier
• Published: University of Liverpool 2008
• Subjects: 541.39
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.490608

Experimental observations have shown that haloalkane molecules, e.g. l-cWorododecane, physisorbed on Si(111)-(7 x 7) self-assemble to form dimers stable to 100° C which corral silicon adatoms. The corral size is governed by the haloalkane chain-length. Spectroscopic and theoretical evidence shows that the haloalkane dimer induces electron transfer to the corralled adatom. The enclosed silicon adatom, within a bistable dimeric corral of self-assembled chlorododecane molecules, switches its energy levels permanently (Type-II corrals) or discontinuously (Type-I corrals). Both types of corral, switching and stable, can be seen to alter the local surface charge distribution. Density Functional Theory and electron transport (STM) simulations of the switch and the stable molecular configurations can help the theoretical understanding of both phenomena in order to characterized the exact molecular conformations that produce field effects to the corralled silicon adatom and local surface charge distribution. Chiral heterogeneous catalysts are mostly fabricated from chiral molecules on a metal support. They playa crucial role in intermediate reactions in the fabrication of pharmacies, itself and important part of today's health econolPY. However, the key parameters in the fabrication of these catalysts, a requirements for their rational design, are still poorly understood despite years of experimental research. In essence, such an understanding can only come from high-level simulations. Here, we present the first predictions about the structure of such a catalyst, tartaric acid on a copper support, over the whole phase space of temperature and coverage. Interestingly, we find that molecular vibrations playa key role in the ensuing ordered structures, and that tuning the fabrication temperature should allow for a wide range of molecular separations, which can be targeted at specific molecules and reactions in chiral heterogeneous catalysis.