title: Born-Haber cycle for monolayer self-assembly at the liquid-solid interface: assessing the enthalpic driving force.
abstract: The driving force for self-assembly is the associated gain in free energy with decisive contributions from both enthalpy and entropy differences between final and initial state. For monolayer self-assembly at the liquid-solid interface, solute molecules are initially dissolved in the liquid phase and then become incorporated into an adsorbed monolayer. In this work, we present an adapted Born-Haber cycle for obtaining precise enthalpy values for self-assembly at the liquid-solid interface, a key ingredient for a profound thermodynamic understanding of this process. By choosing terephthalic acid as a model system, it is demonstrated that all required enthalpy differences between well-defined reference states can be independently and consistently assessed by both experimental and theoretical methods, giving in the end a reliable value of the overall enthalpy gain for self-assembly of interfacial monolayers. A quantitative comparison of enthalpy gain and entropy cost reveals essential contributions from solvation and dewetting, which lower the entropic cost and render monolayer self-assembly a thermodynamically favored process.
authors.affiliation: Deutsches Museum , Museumsinsel 1, 80538 Munich, Germany.
authors.forename: Wentao
authors.initials: W
authors.lastname: Song
authors.forename: Natalia
authors.initials: N
authors.lastname: Martsinovich
authors.forename: Wolfgang M
authors.initials: WM
authors.lastname: Heckl
authors.forename: Markus
authors.initials: M
authors.lastname: Lackinger