Studies of the structure and growth mode of dotriacontane films by synchrotron x-ray scattering and molecular dynamics simulations

doi: 10.1088/0953-8984/16/29/005We report on synchrotron x-ray scattering experiments and molecular dynamics simulations of the structure and growth mode of dotriacontane (n-C32H66 or C32) films adsorbed on Ag(111) and SiO2-coated Si(100) substrates. On the SiO2 surface, the x-ray measurements confirm a structural model of the solid film inferred from high-resolution ellipsometry measurements in which one or two layers of C32 adsorb with the long axis of the molecule oriented parallel to the interface followed by a monolayer in which the molecules have a perpendicular orientation. At higher C32 coverages, preferentially oriented bulk particles nucleate, consistent with a Stranski-Krastanov growth mode. On the Ag(111) surface, we again observe one or two layers of the 'parallel' film but no evidence of the perpendicular monolayer before nucleation of the preferentially oriented bulk particles. We compare the experimentally observed structures with molecular dynamics simulations of a multilayer film of the homologous C24 molecule.This work was support by US National Science Foundation under Grant Nos. DMR-9802476 and DMR-0109057. The Midwest Universities Collaborative Access Team (MUCAT) sector at the Advanced Photon Source (APS) is supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), through Ames Laboratory under ContractNo.W-7405-Eng-82. Use of the APS was supported by the DOE BES under Contract No. W-31-109-ENG-38

Structure and phase transitions of monolayers of intermediate-length n-alkanes on graphite studied by neutron diffraction and molecular dynamics simulation

doi:10.1063/1.3212095We present evidence from neutron diffraction measurements and molecular dynamics (MD) simulations of three different monolayer phases of the intermediate-length alkanes tetracosane (n-C24H50 denoted as C24) and dotriacontane (n-C32H66 denoted as C32) adsorbed on a graphite basal-plane surface. Our measurements indicate that the two monolayer films differ principally in the transition temperatures between phases. At the lowest temperatures, both C24 and C32 form a crystalline monolayer phase with a rectangular-centered (RC) structure. The two sublattices of the RC structure each consists of parallel rows of molecules in their all-trans conformation aligned with their long axis parallel to the surface and forming so-called lamellas of width approximately equal to the all-trans length of the molecule. The RC structure is uniaxially commensurate with the graphite surface in its [110] direction such that the distance between molecular rows in a lamella is 4.26?� = mathag, where ag = 2.46?� is the lattice constant of the graphite basal plane. Molecules in adjacent rows of a lamella alternate in orientation between the carbon skeletal plane being parallel and perpendicular to the graphite surface. Upon heating, the crystalline monolayers transform to a "smectic" phase in which the inter-row spacing within a lamella expands by ~10% and the molecules are predominantly oriented with the carbon skeletal plane parallel to the graphite surface. In the smectic phase, the MD simulations show evidence of broadening of the lamella boundaries as a result of molecules diffusing parallel to their long axis. At still higher temperatures, they indicate that the introduction of gauche defects into the alkane chains drives a melting transition to a monolayer fluid phase as reported previously.This work was supported by U.S. National Science Foundation under Grant Nos. DMR-0411748 and DMR-0705974

Slow Diffusive Motions in a Monolayer of Tetracosane Molecules Adsorbed on Graphite

http://link.aip.org/link/?APCPCS/708/201/1Monolayers of intermediate-length alkane molecules such as tetracosane (n-C24H50 or C24) serve as prototypes for studying the interfacial dynamics of more complex polymers, including bilayer lipid membranes. Using high-resolution quasielastic neutron scattering (QNS) and exfoliated graphite substrates, we have investigated the relatively slow diffusive motion in C24 monolayers on an energy/time scale of ~1-36 µeV (~0.1-4 ns). Upon heating, we first observe QNS in the crystalline phase at ~160 K. From the crystalline-to-smectic phase transition at ~215 K to a temperature of ~230 K, we observe the QNS energy width to be dispersionless, consistent with molecular dynamics simulations showing rotational motion of the molecules about their long axis. At 260 K, the QNS energy width begins to increase with wave vector transfer, suggesting onset of nonuniaxial rotational motion and bounded translational motion. We continue to observe QNS up to the monolayer melting temperature at ~340 K where our simulations indicate that the only motion slow enough to be visible within our energy window results from the creation of gauche defects in the moleculesThis work was supported by the National Science Foundation (NSF) under Grant Nos. DMR-9802476 and DMR-0109057, by the Chilean government under FONDECYT Grant No. 1010548, and by the U. S. Department of Energy through grant DE-FG02-01ER45912. The neutron scattering facilities used in this work are supported in part by the NSF under Agreement No. DMR-0086210