 Polymer overlap concentration

The overlap concentration is the concentration at which distinct dilute polymer coils first substantially interpenetrate. It corresponds to roughly one chain per coil volume. If a chain contains $N$ repeat units, has molar mass $M$ and occupies a coil volume $V_{\mathrm{coil}}$, then its chain number density is approximately $1/V_{\mathrm{coil}}$, its repeat-unit number density is $N/V_{\mathrm{coil}}$, and its mass concentration is $M/(N_A{V}_{\mathrm{coil}})$. A scaling convention uses $V_{\mathrm{coil}}\sim R^3$; a commonly chosen geometric convention uses $V_{\mathrm{coil}}=4\pi R_g^3/3$. These give different order-one prefactors because a coil has no sharp surface. For an ideal chain, $R\sim b{N}^{1/2}$ and a site-volume estimate $v_0\sim b^3$ gives overlap volume fraction ${\varphi }^{\ast }\sim N^{-1/2}$. A good solvent chain with the Flory approximation $R\sim b{N}^{3/5}$ instead gives ${\varphi }^{\ast }\sim N^{-4/5}$.