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Choose the one-particle states of a hydrogen atom, or a central-field description of a chemical atom, with labelsThe principal quantum number $n$ identifies the electron shell. The orbital angular momentum label $\ell$ identifies the electron subshell; the magnetic quantum number $m_{\ell }$ labels $2\ell +1$ independent spatial orbitals. Each has two spin one-half along an axis choices, hence $2(2\ell +1)$ spin orbitals. Applying the Pauli exclusion principle once per spin orbital givesThese quantum numbers label wavefunctions and spin projections, not electron trajectories. They need not resolve exact energy eigenstates in the presence of spin-orbit interaction; changing to coupled angular momentum eigenstates preserves the count of independent one-particle states within this shell model.

For example, $n=3$ allows $\ell =0,1,2$, conventionally $3s,3p,3d$. Their spatial orbital counts are $1,3,5$; their spin orbital counts are $2,6,10$. The sum is eighteen. The algebra behind “one per complete state” is short: two-particle antisymmetrization gives $u\wedge u=(u\otimes u-u\otimes u)/\sqrt{2}=0$, and the zero vector cannot be a normalized quantum state. Opposite-spin electrons in the same spatial orbital have distinct complete states, so their antisymmetric product survives.

This supplies a structural link to the periodic table: finite electron subshell capacities make repeated patterns of occupied electron configurations possible. It does not predict the exact ground state electron configuration or energy of a many-electron chemical atom. Different electron subshells overlap in energy, and electron interactions change their ordering. In particular, the periodic table period lengths are not simply successive $2n^2$ values: the third periodic table period has eight chemical elements, although the full $n=3$ electron shell has eighteen available states. A capacity counts available spin orbitals; an actual filling order requires a Quantum Hamiltonian.

A Slater determinant extends two-particle antisymmetrization to $N$ fermions. Here $x_i$ contains position and spin or other internal variables. Distinct orthonormal one-particle states give the normalized wavefunction displayed in the title. Repeating a one-particle state repeats a column of the determinant, so the wavefunction vanishes. Exchanging particle slots exchanges rows and reverses its sign. A general fermionic quantum state can be a quantum superposition of Slater determinants; it need not be one Slater determinant.

In 1925, Wolfgang Pauli connected two puzzles: alkali metal doublets and their anomalous Zeeman effect, and the capacities of closed electron shells. His paper assigned the extra two-valued property to the optically active electron, rather than an angular momentum of the closed core. Its Paschen-Back effect classification used four quantum numbers; these historical labels should not be identified literally with modern $n,\ell ,m_{\ell },m_s$. The exclusion rule forbade matching all four. This connected resolved one-electron states with closed-group populations. An additional test was the missing triplet counterpart of the equivalent two-$s$-electron ground state in alkaline earth metals. Pauli explicitly claimed counts of allowed states, not their energies or ordering.^[ref]

The modern question is especially concrete: if a Quantum Hamiltonian has a lowest one-particle state, why cannot every electron occupy it? Minimizing energy answers which of the allowed quantum states is preferred; the Pauli exclusion principle determines which quantum states are allowed in the first place. Spectral lines then test energy differences between allowed multiparticle quantum states. A line count is not itself a direct count of occupied spin orbitals: transitions also depend on selection rules and the prepared quantum state populations. The observed anomalous Zeeman effect supplied constraints for the historical classification; the two-particle antisymmetrization below supplies the modern mathematical explanation of exclusion.