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The four Pauli matrices form an orthogonal basis of $2\times 2$ matrices for the Hilbert-Schmidt inner product, since $\mathrm{Tr}({\sigma }_{\mu }{\sigma }_{\nu })=2{\delta }_{\mu \nu }$. A Hermitian density matrix therefore has real coefficients in this basis, and its trace-one condition fixes the identity coefficient. ThusThe multiplication rule for the Pauli matrices ${\sigma }_i{\sigma }_j={\delta }_{ij}I+i{ϵ}_{ijk}{\sigma }_k$ implies $(n\cdot \sigma {)}^2=\Vert n{\Vert }^{2}I$. Its trace is zero, so for $n\ne 0$ its eigenvalues are $\pm \Vert n\Vert$; for $n=0$ it vanishes. HencePositivity is equivalent to $\Vert n\Vert \le 1$. Conversely every real vector in this unit ball defines a positive trace-one matrix by the boxed formula. Therefore $\Phi (\rho )=n$ is a one-to-one correspondence with the Bloch ball, with the displayed inverse. Each coordinate is linear in $\rho$, proving the affine property under any convex mixture.

A density matrix is pure precisely when its eigenvalues are $1,0$, equivalently when ${\rho }^2=\rho$. The eigenvalue formula makes this equivalent to $\Vert n\Vert =1$. Alternatively $\mathrm{Tr}{\rho }^2=(1+\Vert n{\Vert }^2)/2$. Thus the pure states correspond exactly to the Bloch sphere.

For $n\ne 0$, put $\hat{n}=n/\Vert n\Vert$. The spectral projectors for the larger and smaller eigenvalues areThey are orthogonal rank-one projections, have sum $I$, and give $\rho ={\lambda }_{+}{P}_{+}+{\lambda }_{-}{P}_{-}$. For normalized eigenvectors in this nondegenerate case they equal $|{\varphi }_1⟩⟨{\varphi }_1|$ and $|{\varphi }_2⟩⟨{\varphi }_2|$. Their Bloch vectors are therefore $\boxed{n_1=n/\Vert n\Vert ,n_2=-n/\Vert n\Vert }$, the antipodal eigenprojectors of a qubit density matrix.

At $n=0$, the state is $I/2$ and both eigenvalues coincide. There is no distinguished direction and the printed directional expression is undefined. Any orthonormal eigenbasis gives an antipodal pair of pure-state Bloch vectors, since its two projectors sum to $I$, but that pair can point in any direction. The nonzero-$n$ qualification is essential. The PDF denominators are $\Vert n\Vert$, not the converted TeX denominators involving $n_1,n_2$.