Temperature-Resolved Determination of the London Dispersive Surface Energy and Interfacial Separation in Solid Materials

The London dispersive component of surface energy ( ) is a fundamental interfacial parameter governing van der Waals interactions between solid materials and surrounding molecules. Its accurate determination is essential for understanding and controlling a wide range of processes, including adhesion, wetting, catalysis, tribology, pharmaceutical formulation, nanomedicine, as well as energy and environmental technologies. Despite decades of investigation, the reliable determination of for solid materials remains a major challenge. Conventional approaches, such as contact angle measurements and calorimetric methods, are generally limited to well-defined planar surfaces or specific material systems. In contrast, inverse gas chromatography (IGC) has emerged as a powerful and versatile technique for characterizing powders, fibers, and porous solids. In this work, a rigorous thermodynamic framework is developed based on the Hamaker constant, enabling the intrinsic determination of the dispersive surface energy of oxide materials. A key advance lies in the explicit incorporation of the temperature-dependent intermolecular separation distance , extracted from inverse gas chromatography measurements of n -alkane adsorption. Application to a series of oxides (Al 2 O 3 , SiO 2 , ZnO, TiO 2 , and MgO) reveals a consistent hierarchy of dispersive surface energies, governed primarily by electronic polarizability and surface dielectric screening. While the Hamaker constant exhibits only weak temperature dependence, the observed variation of is shown to arise predominantly from changes in interfacial configuration through . This demonstrates that thermal effects on dispersive interactions are controlled by structural fluctuations rather than intrinsic electronic properties. The proposed methodology provides a unified description linking microscopic interaction distances to macroscopic surface energetics. It establishes a robust and physically grounded approach for determining dispersive surface energies and offers new insight into the fundamental mechanisms governing adhesion and interfacial interactions in solid materials.