Onsager's Real Cavity model near solid interfaces
奥森格尔的真实腔模型靠近固体界面
Johannes Fiedler, Drew F. Parsons
AI总结 本文提出扩展的奥森格尔真实腔框架,用于描述小分子在介电液体近平面界面处的Casimir-Polder相互作用,通过解析几何腔开口推导出闭合表达式,揭示局部场屏效、腔几何和材料响应对相互作用幅度和形状的共同决定作用。
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我们开发了一种扩展的奥森格尔真实腔框架,用于描述小分子溶解在介电液体中靠近平面界面处的Casimir-Polder相互作用。通过解析解析腔开口的几何,我们推导出闭合表达式,捕捉分子接近表面时相互作用的修改,并平滑连接到渐近介质辅助极限。使用实验确定的介电函数(水、丙醇和PTFE)以及准确的分子极化率(O₂和N₂),我们计算了代表性分子-液体-表面组合的完整距离依赖势能。结果揭示了局部场屏效、腔几何和材料响应共同决定相互作用的幅度和形状,包括从开放腔(z≈z_C)到封闭腔(z≈z_C)的特征转变。除了提供定量预测外,该框架还提供了对液体中色散力的解析透明分解,使能够直接识别底层物理贡献,并高效探索不同系统中的参数依赖性。该方法因此为在连续、局部场修正描述中解释复杂环境中色散相互作用提供了有用的基准。
We develop an extended Onsager real-cavity framework to describe the Casimir--Polder interaction of small molecules dissolved in dielectric liquids near planar interfaces. By analytically resolving the geometry of the cavity opening, we derive closed-form expressions that capture the modification of the interaction as the molecule approaches a surface and connect smoothly to the asymptotic medium-assisted limit. Using experimentally established dielectric functions for water, propanol, and PTFE together with accurate molecular polarisabilities for O$_2$ and N$_2$, we compute the full distance-dependent potential for representative molecule--liquid--surface combinations. The results reveal how local-field screening, cavity geometry, and material response jointly determine both the magnitude and shape of the interaction, including the characteristic transition between open-cavity ($z\lesssim z_{\rm C}$) and closed-cavity ($z\gtrsim z_{\rm C}$) regimes. Beyond providing quantitative predictions, the framework offers an analytically transparent decomposition of dispersion forces in liquids, enabling a direct identification of the underlying physical contributions and an efficient exploration of parameter dependencies across different systems. The approach thus provides a useful baseline for interpreting dispersion interactions in complex environments within a continuum, local-field corrected description.