 Energy populations and evolving relative phases

Suppose a constant Hamiltonian operator has a complete discrete orthonormal basis of energy eigenstates, $H|n⟩=E_n|n⟩$. Expanding an initial pure state and applying the time-evolution operator term by term givesA projective measurement resolving these basis vectors therefore assigns the same Born rule probability $|c_n{|}^2$ to each label $n$ at every time. An energy measurement groups labels sharing the same energy eigenvalue: $P(E)={\sum }_{n:E_n=E}|c_n{|}^2$ is also constant. If $c_m,c_n\ne 0$, their probability amplitude ratio instead evolves asOnly energy differences enter this relative quantum phase. Adding a constant $\epsilon I$ to the Hamiltonian operator multiplies the entire pure state by $e^{-i\epsilon t/\hslash }$, a global phase, and leaves the density operator unchanged.

For a fixed observable $A$, the expectation value can nevertheless vary:Terms joining distinct energy eigenvalues can oscillate; diagonal terms cannot. If $[A,H]=0$, these terms between different energies vanish, so the expectation value is constant. This distinguishes conservation of energy from the stronger claim that every observable is stationary.

An energy eigenstate has only a global phase evolution and is a stationary state. A quantum superposition entirely within one degenerate energy eigenspace is also an energy eigenstate and is stationary. For a general density operator in finite dimension, stationarity under a constant Hamiltonian operator means $[H,\rho ]=0$: differentiating $U\rho U^{†}$ proves necessity, and commuting $\rho$ through the exponential proves sufficiency. Merely fixing the diagonal energy populations does not fix the off-diagonal quantum coherence.