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Heat capacity at fixed volume is $C_V=(\partial E/\partial T{)}_{V,N}=T(\partial S/\partial T{)}_{V,N}$. From the Helmholtz free energy differential $dF=-SdT-PdV$ at fixed particle number, equality of mixed derivatives gives $(\partial S/\partial V{)}_T=(\partial P/\partial T{)}_V$. Differentiating once more givesFor the canonical partition function, $F=-k_{B}T\log Z$, $E=k_B{T}^2{\partial }_T\log Z$, and $S=k_B(\log Z+T{\partial }_T\log Z)$. Thus, for $V>aN$,andNo Stirling approximation is needed. The heat capacity is independent of volume, while the pressure is linear in temperature, so both sides of the Maxwell-derived identity vanish.

The specific Helmholtz free energy $\psi =U-\theta \eta$ satisfies $d\psi ={\rho }_0^{-1}{P}_{Ii}d{F}_{iI}-\eta d\theta -{\rho }_0^{-1}{f}_{r}d{\xi }_r$. For the multiplicative decomposition of the deformation gradient $F=F_{\ast }A$, adopt $P_{Ji}^{\ast }={\rho }_0\partial \psi /\partial (F_{\ast }{)}_{iJ}$, consistently with the material-first nominal stress tensor. Differentiating $F_{\ast }=F{A}^{-1}$ givesConsequentlyorThese relations follow from the chain rule; the transpose convention matters.

Differentiating the dissipation potential, with the Frobenius norm of $Q$, givesAn integrating factor yields the exponential memory from tensor relaxation:For $n>0$, the driving term is continuously zero at $Q=0$.

Taking the product $T=PF$ explicitly defined in the question, $F=F_{\ast }A$ gives $T=QA$, and hence its requested history functional isThere is a naming error in the PDF: with its $P_{Ii}$ convention, the actual second Piola-Kirchhoff stress tensor is $S=P{F}^{-T}$, while $PF=SC$ is the transpose of the Mandel stress tensor, where $C=F^{T}F$. Thus $S=QA{C}^{-1}$ if that stress measure is required. This agrees with the stress push-forward used in Question 5; the printed product is fully determined by the history above, whereas recovering $S$ also requires the deformation or an invertible elastic constitutive relation.

The multiplicative decomposition of the deformation gradient is used on histories where $A$ stays invertible. Thermodynamic admissibility additionally requires $\mathrm{tr}(Q\dot{A})=\alpha \Vert Q{\Vert }^{n+1}-\mathrm{tr}(AQ)/\tau \ge 0$: positivity of the constants alone does not ensure this for arbitrary prescribed histories.

At $U=0$, use fermionic Matsubara frequencies ${\omega }_r=(2r+1)\pi /\beta$. The fermionic Gaussian integral has inverse propagator $-i{\omega }_r+{\xi }_{\mathbf{k}}$. With its thermal normalization, the determinant for one single-particle level is $1+e^{-\beta \xi }$, as also follows from its empty and occupied states. Two spin species therefore giveThe expression labeled Helmholtz free energy in the PDF is the grand potential, since the trace contains $H-\mu \hat{N}$. The thermodynamic Helmholtz free energy at a prescribed electron number $N_e$ is $F={\Omega }_0+\mu N_e$, with $\mu$ fixed by $N_e=2{\sum }_{\mathbf{k}}{n}_F({ϵ}_{\mathbf{k}})$. The Matsubara determinant requires a normalization prescription; a raw infinite sum of logarithms is not an ordinary convergent sum.

Use inverse temperature ${\beta }_T=(k_{B}T{)}^{-1}$, reserving $\beta$ without a subscript for the critical exponent. Write $c=qJ$; each undirected bond occurs once, so the number of bonds is $Nq/2$. In the mean-field theory of the Ising model, write each Ising spin as ${\sigma }_i=m+\delta {\sigma }_i$ and neglect the product of fluctuations:The resulting independent-spin statistical Hamiltonian isThe constant corrects the double counting of interaction energy. The Ising spin sums now factorize and can all be evaluated:This is the approximate partition function at an assumed mean field; equilibrium fixes $m$ self-consistently. The corresponding Ising auxiliary mean-field free energy isIts equilibrium value gives the mean-field Helmholtz free energy in the imposed field. Away from a stationary point its parameter $m$ is an assumed field variable, not necessarily the actual mean Ising spin of that independent-spin distribution.

For the full small-$m$ expansion at fixed $h$, set $t_h=\tanh ({\beta }_{T}h)$ and $s_h={\mathrm{sech}}^2({\beta }_{T}h)$. Differentiating $\log \cosh z$ gives successive derivatives $t_h$, $s_h$, $-2t_h{s}_h$, and $2s_h(2-3s_h)$ at $z={\beta }_{T}h$. ThereforeAt zero field, spin inversion symmetry eliminates odd powers and this simplifies toThe quadratic coefficient changes sign and the quartic coefficient is positive atThus the zero-field mean-field prediction is a continuous, continuous phase transition: the stable zero spin magnetization develops two symmetry-related nonzero minima continuously below $T_c$.

Both requested routes give the same mean-field self-consistency equation. First, the one-spin expectation in the effective field isSecond, differentiating the Ising auxiliary mean-field free energy giveswhose stationary condition is precisely that mean-field self-consistency equation. Choose its stable, lowest-free-energy branch rather than every algebraic solution.

An equally useful mean-field approximation parametrizes the trial distribution by its actual mean Ising spin. Its probabilities are $(1\pm m)/2$, giving the Bragg-Williams free energy of the Ising modelThis energy-minus-entropy function has expansionIts stationary equation is $h=k_{B}T\mathrm{arctanh}m-cm$, again equivalent to the mean-field self-consistency equation. The two functions differ away from equilibrium, but agree on stationary branches: for $z={\beta }_T(h+cm)$ and $m=\tanh z$, the entropy bracket equals $mz-\log (2\cosh z)$. Their small-$m$ coefficients therefore need not agree at arbitrary temperature; at $T_c$ they have the same leading critical quartic coefficient $c/12$. This distinction prevents confusing the auxiliary-field expansion with the physical-magnetization variational expansion.

For the order-parameter critical exponent, expand the equation of state at $h=0$:On a nonzero stable branch,Hence $\beta =1/2$. The spontaneous magnetization is understood by selecting a branch with an infinitesimal field after the thermodynamic limit; a finite symmetric sample has zero exact zero-field mean Ising spin.

For the magnetic susceptibility per site, define $\chi =\partial m/\partial h$ with $h$ in energy units. Implicit differentiation givesAbove $T_c$, $m=0$ and $\chi =1/[k_B(T-T_c)]$. Below $T_c$, evaluated on a selected ordered branch, the expansion of $m^2$ gives $\chi \sim 1/[2k_B(T_c-T)]$. Thus the magnetic-susceptibility critical exponent is $\gamma =1$ on both sides, with different amplitudes. At $T=T_c$, the equation of state becomesso the critical-isotherm exponent is $\delta =3$. These are mean-field critical exponents, not a claim that neglecting fluctuations gives the exact Ising transition in every dimension.

The statistical Hamiltonian in this question is already in thermal units, as indicated by $e^{-H}$ without an additional ${\beta }_T$. Define $W[h]=\log Z[h]$ and $F[h]=-W[h]$. The mean field and its linear response areThese are functional derivatives of the connected generating functional; the subtraction defines the connected correlation function. In the Landau approximation, neglect loop corrections and evaluate the field integral at a stable saddle $m_h$. It satisfies the Euler-Lagrange equationThis follows by varying the gradient term and integrating by parts, with periodic, decaying, or otherwise appropriate boundary conditions.

The two requested free energy functionals, following the source and Legendre conventions of the question, areIn the scalar-field source Legendre transform on the chosen stable branch, $h$ is chosen to produce $m$, and $\delta {\Gamma }_{\mathrm{L}}/\delta m=h$. Thus the imposed-source Helmholtz free energy and the fixed-order-parameter Gibbs free energy have the appropriate opposite source derivatives. These names are used in the question's magnetic-ensemble convention; the defining sign relation is what fixes the calculation. At leading Landau approximation there is no fluctuation-determinant term in $F_{\mathrm{L}}$.

Differentiate the saddle equation with respect to $h(y)$. The response obeysThereforeEquivalently, the inverse Hessian relation for a connected two-point function states that $G$ is the inverse kernel of ${\delta }^2{\Gamma }_{\mathrm{L}}/\delta m(x)\delta m(y)$. The factor $u_0/2$ follows from twice differentiating the quartic term $u_0{m}^4/4!$; it is not $u_0/6$. This tree-level connected response is obtained by varying the saddle. It does not require replacing the exact connected correlator by a product of the saddle values, which would incorrectly give zero.

For the requested single-momentum formula, assume a homogeneous source and a translationally invariant equilibrium phase, so $m_h(x)=m_0$ and $G(x,y)=G(x-y)$. SetThe Fourier transform with the printed positive sign sends $-{\nabla }^2$ to $q^2$, while the Dirac delta function transforms to one. Hence the Ornstein--Zernike correlation function hasThe inverse convention is $G(x)=\int d^{D}q(2\pi {)}^{-D}{e}^{-iq\cdot x}\tilde{G}(q)$. For general inhomogeneous $h(x)$, $K$ has nonconstant coefficients and $G$ depends separately on its two positions; the displayed momentum-diagonal formula then does not follow. The preceding differential equation still holds in that case.

At zero source and for $u_0>0$, the homogeneous saddle is $m_0=0$ for $r_0>0$, and $m_0^2=-6r_0/u_0$ on either selected stable ordered branch for $r_0<0$. Thus the Landau scalar correlation length isIn the ordered phase the negative bare quadratic coefficient is compensated by the positive curvature at the nonzero saddle. Retaining $m_0=0$ below the transition would instead give an unstable kernel and is not a physical correlation length. With the usual analytic thermal tuning $r_0=a_0(T-T_c)$, $a_0>0$, both branches diverge as $|T-T_c{|}^{-1/2}$, so the correlation-length critical exponent isThe high-temperature amplitude is $\sqrt{2}$ times the low-temperature amplitude for the same $a_0$. This statement is within Landau theory; fluctuations can change critical behavior outside the mean-field regime.

At thermal equilibrium, microscopic reversibility equates the probabilities of a path and its reversed path when both include their Boltzmann distribution initial weights. Denote their endpoint states by $z_1,z_2$, including velocity if needed. Since the Hamiltonian is even under time reversal in classical mechanics,This detailed balance condition and the energy balance for an autonomous Lagrangian yieldThis is the fluctuation-dissipation relation for a Langevin particle: the strength of Gaussian white noise is fixed by the damping and temperature, with $k_B$ the Boltzmann constant.

For an equilibrium coarse-grained variable, the unresolved microscopic states contribute entropy; their statistical weight is encoded in the Helmholtz free energy, rather than in a single microscopic energy. Relative to the same reference measure, ${\rho }_{\mathrm{eq}}(x)\propto e^{-\beta F(x)}$, so microscopic reversibility becomesThis extension assumes an equilibrium coarse-grained description with reversible path statistics; externally driven dynamics need not obey this relation.

Expanding the trace in the spin basis givesso the transfer matrix for the one-dimensional Ising model reproduces the partition function.

In the ordered basis $s=+1,-1$,Its eigenvalues areSince ${\lambda }_{+}>|{\lambda }_{-}|$ at every positive temperature, the thermodynamic limit gives the Helmholtz free energy per spinThis is an analytic function of $T$ and $B$ for $T>0$, so the one-dimensional short-range Ising model has no finite-temperature phase transition.

For one molecule whose translational motion separates from its internal degrees of freedom, the classical one-particle partition function iswhere $q_{\mathrm{int}}$ contains rotational, vibrational, and other internal states. For $N$ indistinguishable noninteracting molecules, the classical ideal-gas partition function is $Z_N=z_1^N/N!$. The thermodynamic pressure therefore obeyssoThe internal structure changes the energy, entropy, and heat capacity through $q_{\mathrm{int}}(T)$, but it does not change the ideal gas law while the internal partition function is independent of volume and the molecules have negligible interactions.

For a dilute monatomic gas $q_{\mathrm{int}}=1$. Using the Stirling formula in $Z_N=(V/{\lambda }^3{)}^N/N!$ and differentiating the Helmholtz free energy $F=-k_{B}T\log Z_N$ gives the Sackur-Tetrode equationWith $N$ fixed, an isentropic process therefore satisfies $V{T}^{3/2}=\text{constant}$, or $T{V}^{2/3}=\text{constant}$. Eliminating $T$ with the ideal-gas law yields the monatomic reversible ideal-gas adiabat

The chemical potential is the change in internal energy when one particle is added at fixed entropy and volume:Equivalently, $\mu =(\partial F/\partial N{)}_{T,V}$ for the Helmholtz free energy.

Let a microstate $s$ have energy $E_s$ and particle number $N_s$. Maximizing the Gibbs entropy subject to normalization and fixed mean values of $E$ and $N$ is the maximum-entropy derivation of equilibrium ensembles. With Lagrange multipliers $\alpha$, $\beta$, and $-\beta \mu$, varyThe stationarity equation is $-\log p_s-1-\alpha -\beta (E_s-\mu N_s)=0$. Normalization therefore gives the grand canonical ensembleHere $\mathcal{Z}$ is the grand canonical partition function and $k_B$ is the Boltzmann constant.

For one fermionic quantum state of energy $\epsilon$, the Pauli exclusion principle permits occupation numbers only $n=0,1$. Its two grand-canonical weights are $1$ and $e^{-\beta (\epsilon -\mu )}$, so its mean occupation is the Fermi-Dirac distribution

For a free nonrelativistic particle, $\epsilon ={\hslash }^2{k}^2/(2m)$. In a region of area $A$, the number of wave-vector states in the annulus from $k$ to $k+dk$, including the two spin angular momentum states, isSince $kdk=(m/{\hslash }^2)d\epsilon$, the two-dimensional free-electron density of states is constant:

We now use units in which $k_B=1$, as in the question. At zero temperature, the Fermi-Dirac distribution is a step function, and henceAt positive temperature the same fixed particle number satisfies the exact relationThusThis is the low-temperature particle-number cancellation for constant density of states. Therefore, for $T\ll {\epsilon }_F$, the mean number of particles in the energy interval $[\epsilon ,\epsilon +d\epsilon ]$ is

Finally, compare the internal energy with its zero-temperature value. The thermally excited particles above ${\epsilon }_F$ and holes below ${\epsilon }_F$ have equal leading particle numbers, so their terms proportional to ${\epsilon }_F$ cancel. With $x=|\epsilon -{\epsilon }_F|/T$,where the integral follows from the fermion-to-boson thermal integral ratio. Differentiation gives the linear low-temperature heat capacity of a two-dimensional Fermi gas:The requested power law is therefore linear in $T$, with exponent one.

Set $k_B=1$. After the Gaussian integral over momenta, the canonical partition function factors aswhereas the ideal gas has $Z_{\mathrm{ideal}}=Z_{\mathrm{kin}}{V}^N/N!$. HenceUsing the Helmholtz free energy $F=-T\log Z$ therefore gives

If $Pdx+Qdy=dF$ for a twice continuously differentiable potential $F$, then $P=F_x$ and $Q=F_y$. Equality of mixed partial derivatives gives the necessary condition for an exact differential:This condition alone does not ensure global exactness on a domain with holes.

For the Helmholtz free energy $A=U-TS$, use the stated identity for internal energy and the product rule:Thus $A_T{|}_V=-S$ and $A_V{|}_T=-p$. Equality of mixed partial derivatives yields the Maxwell relationThe temperature and volume are the independent variables here, with composition and amount of gas fixed.

Next express $S=S(T,V)$ and substitute its total differential into $dU=TdS-pdV$:Matching the coefficient of $dV$ givesThis is the thermodynamic internal pressure identity: an equation of state determines how internal energy changes under an isothermal change of volume.

For the Dieterici equation, set $c=an/(VR)$ while differentiating at fixed $V$. ThenSubstitute into the thermodynamic internal pressure identity. The term proportional to $T$ cancels $p$, leavingThe physical gas domain has $T>0$ and $V>nb$.

For the ideal gas instead, $p=nRT/V$ gives $T(\partial p/\partial T{)}_V-p=0$. Therefore $U$ is independent of volume at fixed amount of gas. Integrating the remaining condition $(\partial U/\partial T{)}_V=C_V$, with constant heat capacity at constant volume, giveswhere $U_0$ is independent of both $T$ and $V$ and fixes the reference for internal energy.

The required Legendre transform is the Helmholtz free energy, $\boxed{F=U-TS}$ up to an additive constant. Its differential is $dF=dU-TdS-SdT=-SdT-pdV$, so $F_T{|}_V=-S$ and $F_V{|}_T=-p$. Equality of mixed partial derivatives for a smooth thermodynamic state gives the Maxwell relationNext use the total differential $dS=S_T{|}_{V}dT+S_V{|}_{T}dV$. Along a fixed-pressure path, divide by $dT$ to get $S_T{|}_p=S_T{|}_V+S_V{|}_T{V}_T{|}_p$. Substitute the Maxwell relation to obtainMultiplying by $T$ gives the usual difference between the heat capacity at constant pressure and the heat capacity at constant volume.

For fixed amount of substance, take the internal energy $U=U(S,V)$. The first law of thermodynamics identifies $T=U_S{|}_V$ and $-P=U_V{|}_S$. Equality of mixed second derivatives givesFor the Helmholtz free energy, subtract the product differential $d(TS)$ from the first law of thermodynamics to obtain $dF=-SdT-PdV$. Its natural variables are $(T,V)$, so $F_T=-S$ and $F_V=-P$. Exactness therefore givesFor the Gibbs free energy, the product rule gives $dG=-SdT+VdP$. Thus $G_T=-S$, $G_P=V$, andFor the enthalpy, $dH=TdS+VdP$, giving $H_S=T$, $H_P=V$ andThese are the four Maxwell relations, each following from exactness in the appropriate pair of natural variables.

For ideal hard spheres, potential energy is zero for nonoverlapping configurations and infinite for overlaps. At fixed temperature and volume, the accessible fluid and crystal configurations therefore have no energetic preference of the ordinary bonding kind: the phase with larger entropy has lower Helmholtz free energy.

Ordering particle centers costs some configurational freedom, but at a high packing fraction it can give each particle more usable cage/free volume than a disordered crowded arrangement. The total number of allowed vibrational and positional configurations can then be greater in a crystal despite its visible long-range order. This is entropy-driven hard-sphere crystallization.

The crystal need not be at close packing. At the stated volume fraction near $0.55$, substantial free space remains for thermal motion. Close packing near $0.74$ is the geometric upper bound for equal spheres, not the fraction at which the crystal first becomes thermodynamically favorable. Treating crystallization as an inevitable decrease in total entropy would confuse visible positional order with the full phase-space count.

The zeroth law of thermodynamics states the transitivity of thermal equilibrium: if two systems each equilibrate thermally with a third, they equilibrate with one another. A reproducible thermometric property can therefore label their temperature. Its empirical numerical scale is not itself the complete thermodynamic content; reversible heat-engine relations establish an absolute temperature scale.

The first law of thermodynamics expresses energy conservation. For a closed system, $dU=\delta Q-\delta W$ when $\delta W$ is work done by the system. internal energy is a state function, while heat and work depend on the path. In reversible simple compressible motion, $\delta W=pdV$ and $dU=TdS-pdV$; an open system additionally needs the energies carried by transferred matter. An ideal gas can expand freely with $Q=W=0$ and unchanged internal energy. The first law alone does not decide whether the reverse spontaneous process occurs.

The Second law of thermodynamics introduces entropy and restricts direction. For a reversible path, $dS=\delta Q_{\mathrm{rev}}/T$; for an irreversible process the entropy balance includes nonnegative production. The entropy of an isolated system cannot decrease. In a cycle, the Clausius inequality is $\oint \delta Q/T\le 0$, using the appropriate boundary/reservoir temperatures. The Kelvin–Planck statement forbids a cyclic device whose sole effect is extracting heat from one reservoir and turning all of it into work; the Clausius statement forbids moving heat from cold to hot with no compensating effect. A refrigerator is allowed because it consumes work. A two-reservoir engine has $\eta \le 1-T_c/T_h$, with equality in the reversible limit. Work may be fully dissipated as heat without contradicting this one-way restriction.

The third law of thermodynamics constrains low-temperature entropy. An equilibrium perfect crystal with a nondegenerate ground state approaches zero entropy as $T\to 0$, fixing the conventional absolute entropy reference. Degenerate ground states or frozen nonequilibrium disorder require care when discussing residual entropy. Under regular equilibrium conditions the heat capacity must decrease sufficiently for $\int C/TdT$ to remain finite; a constant positive classical heat capacity cannot be extrapolated to zero temperature. The unattainability formulation states that absolute zero cannot be reached by a finite sequence of admissible cooling operations. These statements concern the limiting thermodynamic regime, rather than predicting that every substance stays in one classical phase during cooling.

The laws work together: conservation sets a device's energy budget, entropy production restricts the attainable budget, and constitutive equations give the properties of its working material. For fixed temperature and volume, Helmholtz free energy decreases toward equilibrium; at fixed temperature and pressure the corresponding potential is Gibbs free energy. Stable equilibrium, phase coexistence and Maxwell relations follow from these potentials with appropriate constraints. Calorimetry, mechanical-work measurements, thermometry and reversible-path comparisons test different parts of this framework. None of the laws by itself supplies a particular gas equation of state or microscopic heat capacity.

Take $f$ as the tensile force exerted on the band, so reversible stretching supplies work $fdx$. At fixed other mechanical variables,Equality of mixed derivatives of the Helmholtz free energy yields the thermoelastic Maxwell relation for a stretched bandFor entropy-dominated rubber elasticity, increasing extension reduces configurational entropy, consistently giving a tensile force that increases with temperature at fixed extension. A force defined as the band's restoring force on its support has the opposite sign.

For a simple compressible one-component equilibrium system, the fundamental thermodynamic relation isThe internal energy has natural variables $(S,V,N)$: its derivatives give $T$, $-p$ and chemical potential $\mu$. The natural variables of a thermodynamic potential identify the independent arguments whose conjugates appear directly in a potential's differential. A Legendre transform exchanges a variable for its conjugate, giving potentials suited to different controlled conditions:

For fixed composition and the appropriate closed-system constraints, equilibrium minimizes $U$ at fixed $S,V$, $H$ at fixed $S,p$, $F$ at fixed $T,V$, or $G$ at fixed $T,p$, with other allowable internal variations understood. Enthalpy is useful for constant-pressure heat exchange with only pressure–volume work. Helmholtz free energy is suited to fixed-temperature, fixed-volume systems, and Gibbs free energy to fixed-temperature, fixed-pressure phase or chemical equilibrium. Coexisting phases of one substance have equal chemical potentials.

Where a potential is twice continuously differentiable, equality of mixed derivatives gives Maxwell relations. At fixed $N$, the four usual forms areThe fixed subscripts and signs follow from the chosen natural variables. Derivatives through a nonsmooth phase boundary require separate phase descriptions rather than automatic use of the smooth single-phase formulas.

As an application, the Helmholtz relation turns pressure data into an isothermal entropy change. For an ideal gas, $(\partial p/\partial T{)}_V=nR/V$, givingCombining the same relation with $dU=TdS-pdV$ yields $(\partial U/\partial V{)}_T=T(\partial p/\partial T{)}_V-p$, which vanishes for an ideal gas and reveals attractive-energy effects for a van der Waals gas. Thermodynamic potentials organize equilibrium constraints, while Maxwell relations convert difficult entropy derivatives into measurable response derivatives.