title: Chemical and entropic control on the molecular self-assembly process.
abstract: Molecular self-assembly refers to the spontaneous assembly of molecules into larger structures. In order to exploit molecular self-assembly for the bottom-up synthesis of nanomaterials, the effects of chemical control (strength of the directionality in the intermolecular interaction) and entropic control (temperature) on the self-assembly process should be clarified. Here we present a theoretical methodology that unambiguously distinguishes the effects of chemical and entropic control on the self-assembly of molecules adsorbed to metal surfaces. While chemical control simply increases the formation probability of ordered structures, entropic control induces a variety of effects. These effects range from fine structure modulation of ordered structures, through to degrading large, amorphous structures into short, chain-shaped structures. Counterintuitively, the latter effect shows that entropic control can improve molecular ordering. By identifying appropriate levels of chemical and entropic control, our methodology can, therefore, identify strategies for optimizing the yield of desired nanostructures from the molecular self-assembly process.
authors.affiliation: Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai 980-8577, Japan.|Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Kyoto 606-8501, Japan.|Japan Science and Technology Agency (PRESTO), Kawaguchi, Saitama 332-0012, Japan.
authors.forename: Daniel M
authors.initials: DM
authors.lastname: Packwood
authors.affiliation: Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai 980-8577, Japan.|California NanoSystems Institute and Departments of Chemistry and Biochemistry and Materials Science and Engineering, University of California, Los Angeles, Los Angeles, California 90095, USA.
authors.forename: Patrick
authors.identifier: 0000-0002-4901-9592
authors.initials: P
authors.lastname: Han
authors.affiliation: Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai 980-8577, Japan.|School of Materials and Chemical Technology, Tokyo Institute of Technology, Tokyo 152-8352, Japan.
authors.forename: Taro
authors.identifier: 0000-0002-7795-0683
authors.initials: T
authors.lastname: Hitosugi