Past exam of the chemistry A course of the University of Cambridge / 2021 / Paper 2 / A8 / a / i / Solution

The two protons are identical spin-one-half fermions, so the total state is antisymmetric under exchange. In the electronic and vibrational ground state, an even rotational $J$ has a symmetric spatial wavefunction and therefore uses the antisymmetric nuclear-spin singlet state; odd $J$ uses the symmetric triplet state. Thus parahydrogen has one nuclear-spin state, and orthohydrogen has three. Each rotational level also has spatial state degeneracy $2J+1$.

The translational partition functions and all common electronic/vibrational factors cancel in the ratio of equilibrium populations. Using the same zero of energy for the two spin species givesSubtracting the $J=1$ energy separately from all odd levels without restoring that offset in the equilibrium ratio would incorrectly remove the low-temperature preference for parahydrogen. The nuclear spin statistics account for the factor three, independently of the spatial factor $2J+1$.