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The ground electron configuration of caesium has a single $6s$ electron, with $J=1/2$. Addition of angular momentum giving $F=3,4$ fixes the nuclear spin to $I=7/2$. With dimensionless angular momentum operators, write the Fermi contact interaction asThe two hyperfine levels therefore differ by $4A$. In the convention ${\mathbf{\mu }}_I=g_I{\mu }_B\mathbf{I}$ and $g_s\simeq 2$,This exposes a missing ingredient in a prediction from the supplied data: $Z$ and $g_I$ alone do not specify the valence electron contact density. Screening effect and penetration of the closed core strongly affect it. If $g_I$ instead denotes the total nuclear moment in units of ${\mu }_B$, it must first be divided by $I$ in the displayed convention.

An explicitly crude unscreened hydrogen-like ion model uses $|{\psi }_{6s}(0){|}^2=Z^3/(\pi 6^3{a}_0^3)$ and gives ${\nu }_0\simeq 5.76\times 10^{11}\mathrm{Hz}$, or ${\omega }_0\simeq 3.62\times 10^{12}{\mathrm{s}}^{-1}$. It describes neither the shielding nor the radial function of neutral caesium. Using a pure unit-charge $6s$ hydrogen orbital instead gives only $3.46\mathrm{MHz}$, illustrating why a unique useful estimate cannot follow from an unspecified effective charge.

For physical neutral ${}^{133}\mathrm{Cs}$, the independently known zero-magnetic field clock transition isThis measured frequency, used to define the second, is supplementary physical information, not a consequence of $Z=55$ and the rounded $g_I$ alone.^[ref] The direct electronic transition is in the microwave range and is a magnetic dipole transition, rather than a direct optical electric dipole transition. An optical implementation needs a two-field Raman transition.

Using the corrected weak-pulse Ramsey spectrum of part (b), the peak at $\delta =0$ has height $(\Omega {\tau }_p{)}^2$. The quantum interference fringes have spacing $2\pi /T$ in angular frequency, with zeros at $(2k+1)\pi /T$, and the sinc function envelope has its first zeros at $\delta =\pm 2\pi /{\tau }_p$. For $T\gg {\tau }_p$, the central peak has approximately full width at half maximum $\pi /T$ in angular frequency. The clock transition between the two $M_F=0$ states has no first-order Zeeman energy, although a quadratic one remains.

Let the dimensionful angular momentum operators obey $\mathbf{F}=\mathbf{I}+\mathbf{J}$ and take the interaction Hamiltonian as $H^{\prime }=A\mathbf{I}\cdot \mathbf{J}$. Sincethe energy eigenvalues at fixed $I,J$ arewhere $F=|I-J|,\dots ,I+J$. Subtraction gives the Landé interval ruleMany atomic conventions use dimensionless angular momentum operators and call the energy-valued constant itself $A$; then the right-hand side is $AF$. Each energy level has $2F+1$ magnetic sublevels with the same energy in zero field.

For fine structure, the effective interaction is $a_{LS}\mathbf{L}\cdot \mathbf{S}$ with dimensionless angular momentum operators. It originates in the spin-orbit interaction, including the magnetic interaction of electron spin with orbital motion and its relativistic correction. Within an isolated LS coupling atomic term, the labels are the electron configuration, $L,S,J,M_J$, and the interval between adjacent $J$ energy levels is $a_{LS}J$. This is smaller than the electrostatic separation of atomic terms.

For magnetic-dipole hyperfine structure, the nuclear magnetic dipole moment interacts with the magnetic field generated by the electrons. Contributions include the Fermi contact interaction of penetrating $s$ electrons, orbital magnetic fields, and the dipolar field of electron spin. Projected onto one electronic $J$ energy level, their rotationally invariant magnetic-dipole part has the form $a_{IJ}\mathbf{I}\cdot \mathbf{J}$. The labels are $I,J,F,M_F$, together with the approximate electronic labels such as $L,S$. This splitting is generally smaller than fine structure, reflecting the much smaller nuclear magnetic dipole moment. An electric nuclear quadrupole moment can add a different interaction and violate the simple Landé interval rule.

At the larger electrostatic energy scale, an effective two-spin exchange interaction can also be written $a_s{\mathbf{s}}_1\cdot {\mathbf{s}}_2$ within fixed orbitals. Its origin is the Coulomb interaction combined with the Pauli exclusion principle, rather than a large direct magnetic interaction. It separates singlet state and triplet state atomic terms; before spin-orbit coupling, useful labels include the electron configuration, $L,M_L,S,M_S$. General electrostatic atomic term separations need not obey a single Landé interval rule as $L$ varies.

The $4f^7$ shell carries a large spin (its ground atomic term under Hund's rules has $L=0,S=7/2$), and the $6s$ electron penetrates the inner shells. Its nonzero probability density at the atomic nucleus supplies a potentially large Fermi contact interaction with the nuclear magnetic dipole moment. The $6s$ shell here is singly occupied, so the obligatory paired-$6s^2$ cancellation is absent. Both stable europium isotopes have nonzero nuclear spin, as the spectrum below also establishes.

The term symbol ${}^8{D}_{11/2}$ specifies $S=7/2$, $L=2$, $J=11/2$. Its large $J$, combined with appreciable nuclear spin, permits a wide range of total angular momentum $F$ and hence a substantial total hyperfine structure span. For $I=5/2$, $F=3,\dots ,8$ and the span is $30|a|$. The penetrating $6s$ contribution and the available range of $F$ explain the large hyperfine structure; the term symbol alone does not determine its constant, which also depends on electronic recoupling, radial wavefunctions and configuration interaction.