We discuss best N-term approximation spaces for one-electron wavefunctions $\phi_i$ and reduced density matrices ρemerging from Hartree-Fock and density functional theory. The approximation spaces $A^\alpha_q(H^1)$ for anisotropicwavelet tensor product bases have been recently characterized by Nitsche in terms of tensor product Besov spaces. We have used the norm equivalence of these spaces to weighted $\ell_q$ spaces of wavelet coefficients toproof that both $\phi_i$ and ρ are in $A^\alpha_q(H^1)$ for all $\alpha > 0$ with $\alpha = \frac{1}{q} - \frac{1}{2}$ . Our proof is based on the assumption that the $\phi_i$ possess an asymptotic smoothness property at the electron-nuclear cusps.