When reading the Wiki page on differential structures, I'm struck by the exceptional case of $R = 4$.
However, the definition of differential structure leaves me nonplussed, as it seems to just be another name for "maximal atlas" in the context of https://i.stack.imgur.com/MBce6.png, which says: "There is an "essentially unique" smooth structure for any topological manifold of dimension smaller than 4."
When they say "smooth structure" do they simply mean a unique maximal atlas (C-infinity) or is there more to it?
Thanks so much for helping with the clarification.
You are on the right track, but not quite there yet.
First, a smooth structure is indeed nothing more than a maximal $C^\infty$ atlas.
However, to say that the smooth structure is "essentially unique" does not mean that there exists a unique maximal $C^\infty$ atlas. Such a strong uniqueness property is always false: for any smooth manifold $M$ there exists a non-smooth homeomorphism $h : M \to M$, and using $h$ you can then define a different maximal $C^\infty$ atlas by transport of structure, which means replacing your given atlas $\{\phi_i : U_i \to \mathbb R^m\}$ with the new atlas $\{\phi_i \circ h^{-1} : h(U_i) \to \mathbb R^m \}$. For example, even the standard structure on $\mathbb R$ can be changed by transport of structure using the non-smooth homeomorphism $h(x) = \sqrt[3]{x}$.
Instead, for the smooth structure to be "essentially unique" usually means that it is unique up to transport of structure: for any two maximal $C^\infty$ atlases $\{\phi_i : U_i \to \mathbb R^m\}$ and $\{\psi_j : V_j \to \mathbb R^m\}$ there exists a homeomorphism $h : M \to M$, and a bijection between the index sets, such that if $i \leftrightarrow j$ correspond under that bijection then $V_j = h(U_i)$ and $\psi_j = \phi_i \circ h^{-1}$. This, of course, is equivalent to the statement that $h$ is a diffeomorphism from the structure $\{\phi_i : U_ \to \mathbb R^m\}$ to the structure $\{\psi_j : V_j \to \mathbb R^m\}$.