So, for the case of the diamond structure (GaAs, GaN, Si, etc.), the answer is almost already in mg's post#16 : If you know that (0,0,0) and (1/4,1/4,1/4) are the locations of neighboring atoms, then the nearest neighbor spacing d_{nn}=a\sqrt{(1/4)^2 + (1/4)^2 +(1/4)^2 } = a\sqrt{3}/4
If you do not know the positions of atoms in the unit cell, then it's a few steps longer:
1. Refer to this picture:
http://images.google.com/imgres?img...ges?q=diamond+cubic+&svnum=10&um=1&hl=en&sa=N
2. Notice that neighboring atoms are tetrahedrally arranged, with one atom at the vertex and the other at the centroid of the tetrahedron.
3. The centroid of any pyramidal/conical shape is located at 3h/4 from the vertex along the symmetry axis (h is the height).
4. The height of a tetrahedron in h=\sqrt{6}s/3, where s is the side of the tetrahedron.
5. Finally, notice that the other vertices of the tetrahedron lies on face centers, so s=a/\sqrt{2}.
Put these together and see that you get the same result as above.