QM.3 · Exchange symmetry, spin pairs and Pauli exclusion

For identical particles, exchanging every coordinate and spin label changes a fermionic total wavefunction by a minus sign and leaves a bosonic one unchanged. Mathematical slots 1 and 2 label arguments, not permanently distinguishable particles. For two distinct orthonormal orbitals a and b, spatial combinations are Ψ_±=[a(1)b(2)±b(1)a(2)]/√2. Orthogonality makes these combinations normalised and gives exchange eigenvalues ±1. If the two orbitals are identical, the antisymmetric combination is identically zero and the displayed symmetric formula is not correctly normalised; the double-occupation spatial state is simply a(1)a(2). Recheck normalization whenever orbitals or their overlaps change.

For two spatial orbitals a,b and two spin states each, there are four complete single-particle states. Two identical electrons have choose(4,2)=6 occupation patterns: two double-occupation singlets, one different-orbital singlet, and three different-orbital triplets. For three spatial orbitals, there are six complete states and choose(6,2)=15 patterns. Counting ordered assignments overcounts identical particles. Spinless bosons in two orbitals instead have three occupations: both in a, one in each, both in b. These counts assume no additional energy restriction and the stated accessible single-particle states; restricting total energy or spin projection changes the allowed subset.

An antisymmetric spatial state satisfies Ψ_−(x,x)=0, so its joint position density vanishes on the coincidence line. A symmetric spatial state need not vanish there. The difference arises from interference between exchanged amplitudes, even for noninteracting particles; it is not a separately imposed classical repulsive force. For a well of length L, choose a(x)=√(2/L)sin(πx/L), b(x)=√(2/L)sin(2πx/L). At x₁=L/4 and x₂=3L/4, the antisymmetric spatial amplitude is −2/L and its density is 4/L²; the symmetric amplitude is zero. These are joint probability densities per two lengths, not dimensionless probabilities at exact points. Physical spin compatibility still decides which total electronic state uses each spatial combination.

For orthonormal different orbitals a and b, symmetric and antisymmetric spatial states are

A two-electron total state must be antisymmetric under simultaneous exchange of position and spin. Thus symmetric space pairs with the spin singlet; antisymmetric space pairs with triplet spin. If both electrons occupy a, the spatial product is symmetric and only singlet spin is allowed. The different-orbital normalisation formula cannot simply be reused for a = b.