Born-Haber Cycle for Monolayer Self-Assembly at the Liquid-Solid Interface: Assessing the Enthalpic Driving Force

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 liquidsolid 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 BornHaber cycle for obtaining precise enthalpy values for self-assembly at the liquidsolid 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.