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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.