title: Large-scale atomistic simulations of environmental effects on the formation and properties of molecular junctions.
abstract: Using an updated simulation tool, we examine molecular junctions composed of benzene-1,4-dithiolate bonded between gold nanotips, focusing on the importance of environmental factors and interelectrode distance on the formation and structure of bridged molecules. We investigate the complex relationship between monolayer density and tip separation, finding that the formation of multimolecule junctions is favored at low monolayer density, while single-molecule junctions are favored at high density. We demonstrate that tip geometry and monolayer interactions, two factors that are often neglected in simulation, affect the bonding geometry and tilt angle of bridged molecules. We further show that the structures of bridged molecules at 298 and 77 K are similar.
authors.affiliation: Department of Chemical and Biomolecular Engineering, Vanderbilt University, Nashville, Tennessee 37212, USA.
authors.forename: William R
authors.initials: WR
authors.lastname: French
authors.forename: Christopher R
authors.initials: CR
authors.lastname: Iacovella
authors.forename: Peter T
authors.initials: PT
authors.lastname: Cummings
mesh_terms: D001554:Benzene / Q000737:chemistry*; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013499:Surface Properties; D013696:Temperature
chemical_list: C516314:1,4-benzenedithiol; D013438:Sulfhydryl Compounds; D001554:Benzene