For any normalized vector , the Born rule assigns the probability to the corresponding rank-one orthogonal projection. This must be nonnegative for every , which is exactly positive semidefiniteness. For any complete orthonormal basis , the outcome probabilities must sum to one:
Thus a Hermitian matrix represents a physical density matrix only if
These conditions are also sufficient in finite dimension. The spectral theorem writes with and , describing a quantum state ensemble of pure states with valid mixing probabilities. A Hermitian matrix alone could have negative eigenvalues, hence negative measurement probabilities.

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