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The number of sensors, ground-based and remote, exploiting the relationship between soil dielectric response and soil water content continues to grow. Empirical expressions for this relationship generally work well in coarse-textured soils but can break down for high-surface area and intricate materials such as clayey soils. Dielectric mixing models are helpful for exploring mechanisms and developing new understanding of the dielectric response in porous media that do not conform to a simple empirical approach, such as clayey soils. Here, we explore the dielectric response of clay minerals and clayey soils using the mixing model approach in the frequency domain. Our modeling focuses on the use of mixing models to explore geometrical effects. New spectroscopic data are presented for clay minerals (talc, kaolinite, illite and montmorillonite) and soils dominated by these clay minerals in the 1 MHz&ndash, 6 GHz bandwidth. We also present a new typology for the way water is held in soils that we hope will act as a framework for furthering discussion on sensor design. We found that the frequency-domain response can be mostly accounted for by adjusting model structural parameters, which needs to be conducted to describe the Maxwell&ndash, Wagner (MW) relaxation effects. The work supports the importance of accounting for soil structural properties to understand and predict soil dielectric response and ultimately to find models that can describe the dielectric&ndash, water content relationship in fine-textured soils measured with sensors.