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Discarding the photon-number result gives a classical mixture of the two outcome branches. The atomic state, in the basis $(|e⟩,|g⟩)$, isIt is also the reduced state before measuring the field; a nonselective operation on the field does not change the atomic reduced density matrix. The atom is not in a coherent superposition with these populations.

For an atomic energy gap $\hslash \omega$, the thermal population ratio is $p_e/p_g=e^{-\hslash \omega /(k_{B}T)}$. Matching it givesA finite positive temperature exists when $0<p_e<p_g$, with $T\to 0^{+}$ at $p_e=0$ and $T\to +\infty$ as $p_e\to 1/2$ from below. Equal populations correspond to zero inverse temperature. If $p_e>1/2$, the expression is a negative effective temperature for a bounded two-level system, not an equilibrium state at any ordinary positive temperature. For a concrete counterexample to an unrestricted positive-temperature interpretation, at $t=0$ the atom is certainly excited, whereas every positive-temperature Gibbs distribution has $p_e\le 1/2$. The fully excited endpoint is the formal limit $T\to 0^{-}$. Matching one density matrix does not establish genuine thermalization with a bath.

For the canonical quantum Gibbs state,If $H|n⟩=E_n|n⟩$, its spectral form is $\rho =Z^{-1}{\sum }_n{e}^{-\beta E_n}|n⟩⟨n|$, with a sum over any degeneracy and an integral where a continuous spectrum needs one. It is Hermitian, positive and has unit trace, and it commutes with $H$. The formula presumes a well-defined finite partition function. At zero temperature a nondegenerate stable system approaches its ground-state projector; a degenerate ground space requires specifying the ensemble or preparation.

Specify the magnetic coupling before fixing its sign: let the magnetic moment be $\mathbf{\mu }=\gamma \mathbf{S}$, where $\gamma$ is a signed gyromagnetic ratio. The Zeeman effect gives $H_Z=-\gamma \mathbf{B}\cdot \mathbf{S}$. For spin one-half, $\mathbf{S}=\hslash \mathbf{\sigma }/2$, so with $B=|\mathbf{B}|$ and $u=\beta \gamma \hslash B/2$,This is the quantum Gibbs state. Its eigenvalues are $(1\pm \tanh u)/2$, so its purity is $(1+{\tanh }^{2}u)/2$. For nonzero level splitting it approaches a pure state as $|u|\to \infty$: positive inverse temperature selects the lower energy, while negative inverse temperature selects the upper one. It is a maximally mixed state at $u=0$, including infinite temperature or zero magnetic splitting. At zero field the Gibbs state remains $I/2$; lowering temperature alone does not select a unique pure state from that degeneracy.

Negative temperature is meaningful for an internally equilibrated spin sector with a bounded energy spectrum and population inversion. It must be sufficiently isolated from unbounded motional degrees of freedom: the oscillator's unbounded spectrum, for instance, makes its partition sum diverge at negative inverse temperature. The two-level spin partition sum itself stays finite for either sign.

For $\mathbf{B}=B{\mathbf{e}}_z$, the quantum Gibbs state is diagonal in the $S_z$ basis. Its two probabilities are proportional to $e^{\pm \beta \gamma \hslash B/2}$. ThusAt small inverse temperature, $⟨S_z⟩\simeq \beta \gamma {\hslash }^{2}B/4$. As a function of $u=\beta \gamma \hslash B/2$, the normalized spin component is the smooth odd curve $\tanh u$: it crosses zero at $u=0$ and saturates at $\pm 1$. As a function of $\beta$ its direction is reversed if $\gamma B<0$. For $\gamma B>0$, positive temperature favors $S_z=+\hslash /2$, while negative temperature gives the inverted population.

The fixed-particle-number sector is spanned by $|1⟩=c_1^{†}|0⟩$ and $|2⟩=c_2^{†}|0⟩$. In this basis,The relevant quantum Gibbs state is normalized within this two-dimensional sector, not over all particle numbers. With $\beta =(k_{B}T{)}^{-1}$ and $x=\beta t$, the exponential of a Pauli vector givesThereforeIts eigenstates are $|\pm ⟩=(|1⟩\pm |2⟩)/\sqrt{2}$, with energies $\mp t$ and probabilities $p_{\pm }=e^{\pm x}/(2\cosh x)$. These are nonnegative and sum to one, so the matrix is Hermitian and has trace one. Its purity of a density operator isFor $t\ne 0$, the zero-temperature limit is the pure ground-state projector,with purity one. As $T\to \infty$, $x\to 0$ and $\rho \to I/2$, with purity $1/2$. At every strictly positive finite temperature and finite $t$, both eigenvalues are nonzero, so the state is mixed. If $t=0$, the two levels are degenerate and the Gibbs state is $I/2$ at all temperatures, including its zero-temperature limit.

Using dimensionless Von Neumann entropy, $S=-\mathrm{Tr}(\rho \ln \rho )$, givesFor nonzero $t$, $S\to 0$ as $T\to 0$, while $S\to \ln 2$ as $T\to \infty$. More precisely, the high-temperature expansion is $S=\ln 2-x^2/2+O(x^4)$, and the low-temperature form is $S\sim (1+2|x|)e^{-2|x|}$. The thermodynamic entropy includes an overall factor $k_B$.

Take the two magnetic moments along $z$ to be $\pm \mu$, so $H=-\mu B_z{\sigma }_z$ and the two energies are $\mp \mu B_z$. The quantum Gibbs state at inverse temperature $\beta =1/(k_{B}T)$ isIts Bloch vector is $(0,0,\tanh \beta \mu B_z)$. At $B_z=0$, or in the high-temperature limit, it approaches $I/2$; at $T\to 0^{+}$ with nonzero $\mu B_z$, it approaches the lower-energy pure state. Here $\mu$ is the magnitude or signed coefficient multiplying ${\sigma }_z$ in the magnetic Hamiltonian, rather than a moment with an additional unstated factor of two.

A quantum Gibbs state is the density operator of a canonical ensemble with inverse temperature $\beta =1/(k_{B}T)$. It exists when the canonical partition function $Z=\mathrm{Tr}(e^{-\beta H})$ is finite. The spectral theorem assigns probabilities $e^{-\beta E_j}/Z$ to an orthonormal eigenbasis of the Quantum Hamiltonian. An additive constant in the Quantum Hamiltonian cancels between numerator and denominator. For $H=-\mu B{\sigma }_z$, the exponential of a Pauli vector, continued to an imaginary argument, gives ${\rho }_{\beta }=[I+\tanh (\beta \mu B){\sigma }_z]/2$.

Approach of a physical system to thermal equilibrium, usually through interactions with other degrees of freedom. Equality of a reduced density matrix with a quantum Gibbs state at one instant does not alone demonstrate a thermalization mechanism or equilibration over time.