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The nuclear magneton is the unit of magnetic momentwhere $m_p$ is the proton mass. For a nuclear spin operator $\mathbf{I}$, the nuclear magnetic moment is $\mathbf{\mu }=g_I{\mu }_N\mathbf{I}/\hslash$. Consequently its gyromagnetic ratio is ${\gamma }_I=g_I{\mu }_N/\hslash$, and its Larmor frequency in a uniform magnetic field of magnitude $B$ is $|{\gamma }_I|B$. The nuclear magneton is smaller than the Bohr magneton by the electron-to-proton mass ratio.

The nuclear neutron scattering length is the effective length coefficient for low-energy nuclear scattering amplitude. For the elementary coherent calculation below, use a bound coherent coefficient $b_j$ for each site, and neglect absorption so that $b_j$ is real. This coefficient describes the atomic nucleus, including its isotope and nuclear spin dependence; it is not proportional to atomic number. Replacing nuclear coefficients by electronic magnetic moments would describe a different scattering channel, with additional direction and spatial-distribution factors, as explained in magnetic neutron diffraction.

Parahydrogen uses the antisymmetric spin-one-half singlet state,Here $I_{\mathrm{n}}$ labels total nuclear spin; it is not the moment of inertia $I$ in the linear rigid rotor formula. There is one nuclear-spin state for every rotational quantum state. The lowest allowed rotational level is $J=0$, and the next is $J=2$. The description “opposite spins” alone is insufficient: the relative minus sign distinguishes this singlet state from the zero-projection member of the triplet state.

Use the isolated nuclear spin Zeeman effect implied by the supplied nuclear magnetic moment, with hyperfine structure neglected. The proton gyromagnetic ratio isThe two spin levels are separated by $g_p{\mu }_N{B}_0$. Resonant nuclear magnetic resonance therefore requires the Larmor frequency

The duration is a Rabi pi pulse: in a frame rotating with the resonant transverse magnetic field, the spin must rotate through $\pi$. If $B_1$ denotes the magnitude of a circularly rotating field with the correct sense of rotation, the Rabi angular frequency is ${\Omega }_R={\gamma }_p{B}_1$. The shortest pulse is then

There is an amplitude convention to specify. If the applied transverse magnetic field is instead the linearly oscillating $B_1\cos (\omega t)\hat{\mathbf{x}}$, its resonant circular component has magnitude $B_1/2$. The rotating-wave approximation gives ${\Omega }_R={\gamma }_p{B}_1/2$ and henceThe wording does not specify this polarization convention, so the two pulse durations should be distinguished. Odd multiples of either shortest Rabi pi pulse also invert the spin within the corresponding ideal model.

In the Wu experiment, Chien-Shiung Wu and collaborators studied beta-minus decay of polarized cobalt-60,A thin cobalt-60 layer on a cerium magnesium nitrate crystal was cooled by adiabatic demagnetization to a few millikelvin. A polarizing magnetic field produced nuclear polarization. An anthracene scintillation counter and photomultiplier detected the emitted Electrons; angular gamma ray observations from the daughter de-excitation monitored whether the nuclei remained polarized.^[ref]

The Electrons were emitted preferentially opposite the parent nuclear spin. Reversing the nuclear polarization reversed the asymmetry, while warming the sample removed both polarization and the effect. Those controls distinguished a spin-correlated asymmetry from a fixed detector bias.

The relevant angular correlation is a polarized beta-decay angular distribution of the formUnder parity, ${\mathbf{p}}_e\to -{\mathbf{p}}_e$ but $\mathbf{J}\to \mathbf{J}$, so the spin-momentum correlation changes sign. Parity conservation would require equal rates for these two directions relative to the same spin. The observed nonzero coefficient therefore demonstrated parity violation in beta decay. An unpolarized source would average this correlation to zero and could not provide the same test.

Entropy at absolute zero. The Third law of thermodynamics concerns the low-temperature limit of equilibrium states. In the zero-entropy formulation, the entropy of a perfect crystal with a nondegenerate ground state tends to zero as $T\to 0$. The statistical interpretation is $S=k_B\ln \Omega$: a unique accessible ground state has $\Omega =1$. The entropy-difference formulation of the Third law of thermodynamics states that entropy differences associated with regular changes of mechanical parameters tend to zero as absolute zero is approached. These statements require equilibrium and appropriate ground-state assumptions; a frozen disordered material or a degenerate ground state can carry residual entropy.

For a phase of fixed composition and pressure,A finite limiting entropy constrains this integral. Ordinary equilibrium heat capacities therefore vanish as temperature approaches zero, with familiar examples $C\propto T^3$ for three-dimensional acoustic phonons and $C\propto T$ for a normal degenerate Fermi liquid. A constant positive heat capacity extrapolated to zero would give a logarithmically divergent entropy difference and is impossible in this regime. Discontinuous transitions and anomalous limits need separate treatment rather than extending a high-temperature approximation indefinitely.

Gibbs free energy. For fixed particle numbers,Thus, when $S\to 0$, the Gibbs free energy approaches its zero-temperature value with a horizontal tangent:The equality $G(0,p)=H(0,p)$ uses the enthalpy $H=U+pV$; neither limiting value needs to be zero. The low-temperature Gibbs free-energy expansion makes the approach quantitative. For $C_p=a{T}^r$ with $r>0$ and $S(0)=0$,The second derivative is ${\partial }_T^{2}G=-C_p/T\le 0$, although it need not tend to zero. For a reaction between such equilibrium phases, ${\partial }_T\Delta G=-\Delta S\to 0$, and $\Delta G$ and $\Delta H$ approach one another. If a genuine residual entropy $S_0$ is retained instead, $G=G(0,p)-S_{0}T+\cdots$ has limiting slope $-S_0$. A horizontal tangent cannot be asserted without the zero-entropy condition.

Why helium remains a liquid. Helium atoms attract each other weakly and are exceptionally light. Their zero-point energy is large compared with the binding that would localize them in a solid. Both helium-4 and helium-3 can therefore remain liquid down to the lowest temperatures at low pressure; substantial applied pressure is needed to solidify them. This is not a violation of the third law. A quantum liquid can have a unique low-entropy ground state, and zero-point motion does not itself imply thermal entropy. The third law does not require every substance to crystallize at atmospheric pressure.

A helium-4 atom has integer spin zero and is a boson. Below the lambda point near $2.17\mathrm{K}$ at saturated vapor pressure, its liquid is superfluid. Its strong interactions mean that it is not quantitatively an ideal Bose gas, and the condensate fraction need not equal the superfluid fraction. The two-fluid model of superfluidity separates an entropy-carrying normal component of a superfluid from the superfluid component, whose entropy is zero. At sufficiently low temperature the dominant thermal excitations are acoustic phonons: their linear dispersion in three dimensions gives $U-U_0\propto V{T}^4$, $C_V\propto V{T}^3$ and $S\propto V{T}^3$. Higher-energy rotons are exponentially suppressed. Thus the normal component of a superfluid and entropy disappear as $T\to 0$, while superfluid flow and quantum motion can persist.

A helium-3 atom has spin $1/2$ and is a fermion. Well below its Fermi temperature, but above its superfluid transition, liquid helium-3 is a degenerate interacting Fermi liquid. Only quasiparticles close to the Fermi surface are thermally excited, giving $C_V\propto T$ and $S\propto T$. At temperatures of order a millikelvin, helium-3 also becomes superfluid through formation of Cooper pairs of fermions. This is not Bose-Einstein condensation of individual helium-3 atoms. Pairing reorganizes the low-energy excitation spectrum; in the fully gapped bulk B phase, the fermionic quasiparticle contribution to heat capacity is exponentially suppressed at temperatures well below the pairing gap. Gapless collective modes can still give thermal terms following a power law. The entropy nevertheless tends to zero. The normal Fermi-liquid law cannot be extrapolated through its pairing transition unchanged.^[ref]

Helium-3 also illustrates the importance of nuclear spin entropy. Over an intermediate low-temperature range, localized spins in the solid can retain approximately $k_B\ln 2$ of entropy per atom, while the degenerate liquid has much less. Reversible conversion of liquid to the higher-entropy solid then absorbs heat; adiabatic compression along the melting curve can cool the sample. This is Pomeranchuk cooling. At still lower temperature, interactions between the nuclear spins remove this nearly free-spin entropy, so a constant $k_B\ln 2$ cannot be extrapolated to absolute zero.^[ref]

Liquefaction and cooling methods. A gas must be below its liquid-gas critical point to form a distinct liquid phase by compression. Compression above the critical temperature alone cannot achieve ordinary liquid-vapour coexistence. Practical liquefaction removes the compression heat, cools the compressed gas in a heat exchanger and uses expansion to lower its temperature further.

A throttling valve operates approximately at constant specific enthalpy when kinetic-energy changes and heat leakage are negligible. The Joule-Thomson coefficient isusing consistent molar quantities, or consistent total quantities for a fixed amount. A pressure drop cools the gas if ${\mu }_{\mathrm{JT}}>0$. An ideal gas has zero Joule-Thomson coefficient; real intermolecular interactions are essential. In particular, room-temperature helium warms on throttling, so it must first be brought into a region of positive Joule-Thomson coefficient. Expansion through an engine or turbine can instead remove work and produce approximately isentropic cooling.

A regenerative liquefier sends the cold returning gas through a counterflow heat exchanger to precool the incoming compressed gas before its next expansion. Expansion engines and external precooling can supply the initial cooling; repeated operation then produces liquid. Modern helium liquefaction commonly combines work-producing expansion with a final throttle. ^[ref]

Once liquid exists, pumping away vapour lowers its saturation pressure and boiling temperature. The escaping vapour carries latent heat away, cooling the remaining liquid. At still lower temperatures, a dilution refrigerator exploits the different entropy carried by helium-3 in concentrated and dilute helium mixtures; adiabatic demagnetization and Pomeranchuk cooling provide other routes.

Approaching zero. The unattainability formulation of the third law states that regular cooling operations with finite resources cannot reach absolute zero in finitely many stages. As the entropy available to remove becomes small and thermal couplings weaken, each method loses its ability to take the final step. An isentropic cooling trajectory starting at nonzero entropy cannot reach a common zero-entropy endpoint through regular finite changes of parameters. A fully general finite-time claim also requires assumptions about available controls and heat-transfer rates. Quantum liquids and refrigeration methods can approach $0\mathrm{K}$ while remaining consistent with vanishing equilibrium entropy; they do not provide a finite-operation route to absolute zero.

Spin isomers of hydrogen are two forms of molecular hydrogen, ${}^1{\mathrm{H}}_2$, distinguished by the combined nuclear spin of their two protons. They have the same chemical formula and electronic ground state, but different allowed molecular rotation states. Parahydrogen has total nuclear spin zero and even rotational quantum number $J$; orthohydrogen has total nuclear spin one and odd $J$. The difference makes heat capacity a probe of fermionic exchange symmetry, and makes cooling history matter for a tank of molecular hydrogen.

Assume the electronic ground state $X{}^1{\Sigma }_g^{+}$ and the vibrational ground state of a free molecule. The electronic factor is symmetric under exchanging the two protons, and the vibrational factor depends only on their separation, so it is also symmetric. These assumptions concern the exchange of protons; the electronic wavefunction separately obeys fermionic exchange symmetry under exchange of Electrons. Neglect electronic excitation, vibrational excitation, external fields, and small interactions involving nuclear spin when calculating rotational energy eigenvalues.

The two protons are identical particles with spin $1/2$. Their complete wavefunction must change sign under their particle exchange operator. Interchanging the two ends reverses the internuclear direction $\hat{\mathbf{r}}$, and the spherical harmonic rotational factor satisfiesThe antisymmetric spin-one-half singlet state therefore requires symmetric, even-$J$ rotation; the symmetric spin-one-half triplet state requires antisymmetric, odd-$J$ rotation. This is exchange symmetry of two identical spin-one-half fermions applied inside a diatomic molecule, not an extra rotational force. A linear rigid rotor may omit spin-dependent splittings while still requiring this restriction on its allowed quantum states.