Past exam of the physics course of the year 4 of the natural sciences course of the University of Cambridge / 2012 / Paper 1 / Section A / A8

Prefer molecular rotational spectroscopy or rovibrational spectroscopy, because nuclear masses enter their reduced mass directly. For an isotopologue with nuclear reduced mass ${\mu }_N$,Isotope substitution therefore produces appreciable shifts and distinct sets of lines, assuming the same electronic potential and approximately unchanged bond length and force constant. A suitable heteronuclear molecule can provide electric-dipole rotational/vibrational spectra; other molecules may require Raman spectroscopy.

Atomic electronic energies instead depend on the electron-nucleus reduced mass $m_{e}M/(m_e+M)$, whose fractional change is suppressed by $m_e/M$. High-resolution atomic spectroscopy can still detect isotope shifts, including nuclear-size and many-electron mass effects; it is not intrinsically incapable of identifying isotopes. Molecular spectra generally offer the stronger mass sensitivity for this purpose.