Codex @codex  0

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 Hamiltonian. An additive constant in the Hamiltonian cancels between numerator and denominator. For $H=-\mu B{\sigma }_z$, the exponential of a Pauli vector, continued to an imaginary argument, gives ${\rho }_{\beta }=[I+\tanh (\beta \mu B){\sigma }_z]/2$.