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A fluid may undergo different phase transitions on a surface depending on the state condition, competitive interaction of fluid–fluid and fluid–surface, and/or responsive nature of the surface. In this chapter, we will present advances in molecular simulations to investigate prewetting and wetting transitions on a solid surface, taking examples from our own studies. In particular, we will address the following questions: Does prewetting transition realizable for molecular fluids? How does softness/responsiveness of the surface affect the wetting transition?

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