The set of Pauli matrices is a basis for the (real) vector space of complex traceless self-adjoint 2×2 matrices. If we define the inner product on that space by ##\langle A,B\rangle=\operatorname{Tr}(A^*B)##, where * denotes conjugate transpose, then I think the matrices ##E_i=\sigma_i/\sqrt{2}## form an orthonormal basis of that space. (You should check to make sure that I remember this right).