Variations from equilibrium Young’s angle, known as contact angle hysteresis (CAH), are frequently observed upon droplet deposition on a solid surface. This ubiquitous phenomenon indicates the presence of multiple local surface energy minima for the sessile droplet. Previous research primarily explains CAH via considering macroscopic roughness, such as topographical defects, which alter the effective interfacial energy between the fluid phase and the solid phase, thereby shifting the global surface energy minimum. One typical example is the classic Cassie–Baxter–Wenzel theory. Here, we propose an alternative microscopic mechanism that emphasizes the complexity of molecular rearrangements at the fluid–solid interface, treating their interfacial tensions as variables, which results in multiple local surface energy minima. Our theoretical framework demonstrates that CAH can occur even on chemically homogeneous and mechanically smooth-flat substrates, aligning with previously unexplained experimental observations. In addition, we explore the interplay between macroscopic and microscopic roughness in influencing CAH and clarify the contrasting wetting behaviors—the lotus effect and the rose petal effect—on hierarchical roughness from a thermodynamic perspective. This work provides valuable insights into surface tension determination by restoring the natural physical properties of interfaces and illuminates the multifaceted mechanisms underlying the everyday occurrences of CAH.
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