Amphiphile self-assembly dynamics at the solution-solid interface reveal asymmetry in head/tail desorptionElectronic supplementary information (ESI) available: Details of experimental and computational methods. Supplementary data. See DOI: 10.1039/c8cc04465a

• Main Authors: Castillo, Henry D, Espinosa-Duran, John M, Dobscha, James R, Ashley, Daniel C, Debnath, Sibali, Hirsch, Brandon E, Schrecke, Samantha R, Baik, Mu-Hyun, Ortoleva, Peter J, Raghavachari, Krishnan, Flood, Amar H, Tait, Steven L
• Format: Journal Article
• Published: 06.09.2018
• ISSN: 1359-7345; 1364-548X
• DOI: 10.1039/c8cc04465a

Amphiphilic alkoxybenzonitriles (ABNs) of varying chain length are studied at the solution/graphite interface to analyze dynamics of assembly. Competitive self-assembly between ABNs and alkanoic acid solvent is shown by scanning tunneling microscopy (STM) to be controlled by concentration and molecular size. Molecular dynamics (MD) simulations reveal key roles of the sub-nanosecond fundamental steps of desorption, adsorption, and on-surface motion. We discovered asymmetry in desorption-adsorption steps. Desorption starting from alkyl chain detachment from the surface is favored due to dynamic occlusion by neighbouring chains. Even though the nitrile head has a strong solvent affinity, it more frequently re-adsorbs following a detachment event. Asymmetric dynamics in fundamental adsorption and desorption steps drive self-assembly at solution/solid interface.