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Consider two distinguishable, noninteracting two-level systems, each with energies $0$ and $\Delta >0$. Their four microstates $(0,0),(0,1),(1,0),(1,1)$ have total energies $0,\Delta ,\Delta ,2\Delta$. Thus the three energy macrostates have state degeneracies $1,2,1$. This is a stipulated finite model, not a measured material.

Set $q=e^{-\beta \Delta }$. The four individual Boltzmann factors are $1,q,q,q^2$, so the partition function and aggregate probabilities areEach of the two middle microstates has probability $q/Z$, while their shared energy macrostate has probability $2q/Z$.

At the temperature satisfying $\Delta =k_{B}T\ln 2$, the Boltzmann factor is $q=1/2$ and the partition function is $Z=9/4$. ThereforeThe middle energy is as likely as the ground state energy because its state degeneracy is twice as large. Yet each individual middle microstate is only half as likely as the ground state microstate. The diagram places the four energies beside their individual probabilities, then shows the sums within each macrostate.

The expected value of energy follows directly by weighting the three possible energies:At $q=1/2$ this is $2\Delta /3$. An individual energy measurement still returns $0$, $\Delta$ or $2\Delta$; the expected value describes the ensemble average, rather than a fourth possible measured energy.

Take $N=20$ distinguishable, labeled particles and two boxes of equal volume. Retain only whether each particle is in the left or right box: use a bit $0$ for left and $1$ for right. Each length-20 string is one coarse microstate of this toy model. Assume the labels make independent side choices with equal probability, so the $2^{20}=1048576$ strings are equiprobable. Equal volumes motivate these weights for noninteracting particles with no preference for either box; equal volumes alone would not establish them for an arbitrary interacting gas.

Now retain only the number $k$ in the left box as the macrostate. Choosing which $k$ labels are left gives a binomial coefficient, soThe factorials count assignments to labels; the probability of a macrostate sums the probabilities of its constituent microstates. This is the binomial distribution with parameters $20$ and $1/2$. The same binomial coefficient appears in the counting of distinguishable two-level systems, although here the macrostate records occupancy rather than energy. ^[ref]

The largest binomial coefficient occurs at $k=10$, the balanced macrostate. All-left means $k=20$ and supplies just one string. ThusThere are $184756$ balanced strings for every all-left string, even though each individual string has the same probability. Exact balance has about $17.6\%$ of the total probability; equilibrium reasoning concerns the many macrostates near balance too, rather than certainty of exactly ten particles on each side. The diagram compares the counts with their natural logarithms.

Four fair, independent coins give a smaller worked example with the same binomial distribution. If $k$ is the number of heads, the five macrostates $k=0,1,2,3,4$ contain respectively $1,4,6,4,1$ microstates. Their probabilities are respectively $1/16,4/16,6/16,4/16,1/16$. In particular, two heads is one macrostate containing six ordered coin sequences, with Boltzmann entropy $k_B\ln 6$ in this counting analogy. A prescribed ordered sequence has one realization. The next diagram enumerates the same sixteen strings as left/right assignments.

The canonical ensemble is the probability distribution for a system in thermal equilibrium with a heat bath at fixed temperature $T$, with fixed particle number and external parameters. It allows energy exchange, so individual energy measurements fluctuate. With Boltzmann constant $k_B$ and inverse temperature $\beta =1/(k_{B}T)$,The heat bath is idealized as large enough that exchanges barely change its temperature; coupling must permit equilibration while contributing negligible interaction energy. A finite heat bath approximates this description only when its temperature change is negligible over the relevant exchanges. Strong coupling or a small heat bath can require a different description.

For one two-level system at positive temperature, the Boltzmann weights are $1,e^{-\beta \Delta }$, henceAt $\beta \Delta =\ln 3$, $Z_1=4/3$ and $p=1/4$. This is a probabilistic thermal mixed state. For quantum levels, its density matrix is $\rho =(1-p)|0⟩⟨0|+p|1⟩⟨1|$. The pure state $\sqrt{1-p}|0⟩+\sqrt{p}|1⟩$ has the same energy measurement probabilities, but also has quantum coherence between the energy eigenstates. Matching those probabilities does not make the states equivalent.

The partition function $Z(\beta )={\sum }_s{e}^{-\beta E_s}$ is the sum of the Boltzmann weights over individual microstates. Dividing by it makes their probabilities sum to one. When summing distinct energies instead, include the state degeneracy: $Z={\sum }_{E}g(E)e^{-\beta E}$. For two independent distinguishable two-level systems,The middle coefficient counts two microstates, exactly as in the preceding figure. For $N$ such units, $Z_N=Z_1^N$; this factorization requires additive energy and independence, and generally fails with interactions.

The usefulness goes beyond normalization. For fixed energies, derivatives of the natural logarithm of the partition function yield measurable quantities:Here $U$ is internal energy, the second expression is the energy variance, and $S$ is Gibbs entropy. For one two-level system at fixed $\Delta$, its heat capacity $C=\partial U/\partial T$ and entropy areAt $\beta \Delta =\ln 3$, these give $U/\Delta =0.25$, $C/k_B\simeq 0.2263$ and $S/k_B\simeq 0.5623$. For independent units, all three quantities add.

The figure shows why heat capacity peaks. At low temperature, the excited energy is rarely occupied; at high temperature, the probabilities are almost equal and further warming barely changes internal energy. The largest response lies between these limits, at $k_{B}T/\Delta \simeq 0.4168$, where $C/k_B\simeq 0.4392$. Meanwhile entropy rises from zero toward $k_B\ln 2$, reflecting two equally likely alternatives. This high-temperature limit belongs to the stipulated two-level system; extra accessible energy eigenstates would change it.

In a two-level system, let the Hamiltonian operator have matrix $H=\mathrm{diag}(0,2)$ in the orthonormal basis $|0⟩,|1⟩$. The normalized real trial quantum states and their Rayleigh quotient areThe excited-state probability amplitude is $\sin \theta$, so its probability is ${\sin }^2\theta$. Thus $E(\theta )\ge 0=E_0$, with equality if and only if the excited-state probability amplitude vanishes: $\theta \in \pi \mathbb{Z}$. The remaining quantum state is $|0⟩$ up to a global phase. At $\theta =\pi /4$ the trial energy is $1$; at $\theta =\pi /2$ it is $2$. These are upper bounds on the ground-state energy, even though neither is a minimizing trial.

The real trial family contains the ground state, so it attains the exact minimum despite not covering every complex quantum state. More generally, a family covering all normalized vectors in a two-dimensional Hilbert space gives the exact lowest eigenvalue of any Hermitian matrix by minimizing its Rayleigh quotient. For a complex trial $c_0|0⟩+c_1|1⟩$ with $|c_0{|}^2+|c_1{|}^2=1$, the same calculation gives $E=2|c_1{|}^2$: a relative quantum phase cannot change this diagonal Hamiltonian energy. This finite example is the weighted mean proof of the variational method with just two energy eigenstates.

Consider a stipulated dilute collection of independent two-level systems, each with longitudinal magnetic moment $s\mu$, $s=\pm 1$, and energy $E_s=-s\mu B_0$. The prescribed vacuum/applied magnetic flux density is $B_0={\mu }_0{H}_{\mathrm{app}}$. Ignore interactions, orbital magnetic response, and the small sample-field correction. This is the magnetic version of the existing independent spin-one-half two-level system, with alignment probabilities rather than an interacting Curie–Weiss model.

For temperature $T>0$, the canonical ensemble gives the one-moment partition function $Z_1=2\cosh x$, with $x=\mu B_0/(k_{B}T)$. Taking the expected value over its two Boltzmann weights givesHere $n$ is the number density, $k_B$ the Boltzmann constant, and $\tanh$ the hyperbolic tangent. For $|x|\ll 1$, its small-argument expansion of the hyperbolic tangent gives $M\simeq {\mu }_{0}n{\mu }^2{H}_{\mathrm{app}}/(k_{B}T)$, a Curie's law response in the applied-$H$ convention. For large $|x|$, $M$ approaches the saturation magnetization $n\mu$ with sign set by the field, and its differential magnetic susceptibility falls towards zero.

Both plots use stipulated $n=10^{26}{\mathrm{m}}^{-3}$, $\mu =9.2740101\times 10^{-24}\mathrm{J}{\mathrm{T}}^{-1}$, $k_B=1.380649\times 10^{-23}\mathrm{J}{\mathrm{K}}^{-1}$, and ${\mu }_0=1.25663706\times 10^{-6}\mathrm{T}\mathrm{m}{\mathrm{A}}^{-1}$. The moment is approximately one Bohr magneton; the chosen vacuum permeability is a rounded model input. At $T=2\mathrm{K}$, $M_s=927.401\mathrm{A}{\mathrm{m}}^{-1}$ and ${\chi }_{\mathrm{model}}(0)=3.91410\times 10^{-4}$. The linear approximation overestimates $M$ by less than $3\%$ for $|x|\le 0.3$, corresponding to $|{\mu }_0{H}_{\mathrm{app}}|\le 0.89324\mathrm{T}$ or $|H_{\mathrm{app}}|\le 0.71082\mathrm{MA}{\mathrm{m}}^{-1}$. These parameters keep the modeled response weak; neglected magnetic feedback is of relative order ${\chi }_{\mathrm{model}}(0)$, rather than an explanation of a material's ordered phase.

At $B_0=0$, cooling increases the zero-field slope as $1/T$. At fixed $B_0\ne 0$, cooling instead gives ${\chi }_{\mathrm{model}}\sim 4{\mu }_{0}n{\mu }^2{e}^{-2\mu |B_0|/(k_{B}T)}/(k_{B}T)$: a saturated moment can hardly change further. The order of the zero-field and zero-temperature limits matters. This independent model has no finite-temperature collective phase transition; the diverging zero-field slope alone does not establish one.

A macrostate groups microstates sharing prescribed coarse data. The grouping depends on what is retained: here retain only total energy. For the two distinguishable two-level systems, the macrostates $E=0,\Delta ,2\Delta$ have state degeneracies $1,2,1$. Although two units are not macroscopic in size, they make this loss of information visible: knowing $E=\Delta$ does not tell us which unit is excited.

At inverse temperature $\beta \Delta =\ln 3$, each unit's excited-state probability is $p=1/4$. Their independence gives microstate probabilities $9/16,3/16,3/16,1/16$ in the order above. Adding within each macrostate givesThe total expected value of energy is therefore $\Delta (6/16)+2\Delta (1/16)=\Delta /2$, matching two units each with expected value of energy $\Delta /4$. Equal state degeneracies would give the wrong answer: macrostate probabilities combine counting with the Boltzmann factor. At very high positive temperature, all four microstates become equally likely, but these three macrostate probabilities approach $1/4,1/2,1/4$.

A microstate is a complete microscopic specification within the chosen model. For two distinguishable, noninteracting two-level systems, label the units $A,B$ and their states $0,1$, with energies $0,\Delta$ and $\Delta >0$. The four microstates arewith total energies $0,\Delta ,\Delta ,2\Delta$. Distinguishability matters: $(0,1)$ and $(1,0)$ describe different assignments to the labeled units. Noninteraction matters too: their energies add without an extra coupling term.

For a classical particle model, a microstate can instead be a point in phase space, specifying every position and momentum. In the quantum canonical ensemble, the sum uses energy eigenstates; a general quantum state may also contain quantum coherence, which an energy label alone does not specify.

Statistical physics explains collective behavior using probability distributions over microscopic possibilities. Its central surprise is that incomplete microscopic knowledge can still produce precise predictions for internal energy, entropy and heat capacity. The bridge is statistical mechanics: specify the available microstates, assign their probabilities, then compute the expected values of measured quantities.

A two-level system already displays the idea. Warming it makes its higher energy more likely; its heat capacity first rises, then falls as the two probabilities approach equality. With two distinguishable units, merely counting microstates explains why the middle energy has twice the state degeneracy. These small examples expose the machinery before the much larger sums needed for a photon gas or an Ising model.

The appeal is economical: the same microscopic energies and probabilities explain both an average reading and its variance. A measurement's spread therefore becomes useful physical information rather than an inconvenience to discard.

Take an isolated two-level system, or a spin one-half qubit, with Pauli matrices ${\sigma }_x,{\sigma }_z$. Let ${\sigma }_z|0⟩=|0⟩$ and ${\sigma }_z|1⟩=-|1⟩$. The initial and final Hamiltonian operators areThe energy gaps are ${\Delta }_i,{\Delta }_f$. Prepare the initial ground state $|0⟩$, with energy eigenvalue $-{\Delta }_i/2$. A final orthonormal eigenbasis isDirect matrix multiplication gives $H_f|g_f⟩=-{\Delta }_f|g_f⟩/2$ and $H_f|e_f⟩=+{\Delta }_f|e_f⟩/2$. The unchanged initial quantum state is $|0⟩=c|g_f⟩-s|e_f⟩$. Its new probability amplitudes are the inner products $c,-s$; the Born rule gives $p_g=c^2,p_e=s^2$. The angle between the real amplitude vectors is $\theta /2$, whereas the Hamiltonian axis on the Bloch sphere rotates through $\theta$.

At $\theta =\pi /3$, $c=\sqrt{3}/2$ and $s=1/2$, so the final energy measurement gives $-{\Delta }_f/2$ with probability $3/4$ and $+{\Delta }_f/2$ with probability $1/4$. At $\theta =0$ the initial ground state remains the final ground state; at $\theta =\pi$ it is the final excited energy eigenstate. These statements are about the new energy labels, not an instantaneous physical rotation of the quantum state.