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Use rovibrational spectroscopy combination differences so that the band origin cancels. With the assignments above, $R(2)$ and $P(4)$ end at the same upper level $J^{\prime }=3$, givingLikewise $R(3)$ and $P(3)$ start at the same lower level $J=3$, soOnly the printed wavenumbers are needed:Thus $B^{\prime }-B^{\prime \prime }\simeq 0.00429{\mathrm{cm}}^{-1}$. The rotational constants differ only slightly, so the average moment of inertia changes little on vibrational excitation. The upper value is slightly larger, corresponding to a slightly smaller effective moment of inertia. This sign is possible for a bending excitation; the intuition that excitation must always lengthen a diatomic bond is not a general rule for a polyatomic bend.

The rounded printed values are internally consistent: fitting all six positions to the same elementary model gives approximately ${\tilde{\nu }}_{\ast }=711.9945{\mathrm{cm}}^{-1}$, $B^{\prime \prime }=1.47797{\mathrm{cm}}^{-1}$ and $B^{\prime }=1.48203{\mathrm{cm}}^{-1}$, with residuals below $0.002{\mathrm{cm}}^{-1}$. The displayed combination-difference values have more digits than their physical accuracy; the meaningful scale is about $1.48{\mathrm{cm}}^{-1}$.

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.

The rovibrational spectroscopy branch in which absorption lowers the total rotational angular momentum quantum number by one. A label $P(J)$ conventionally specifies the lower-state value $J$.

The rovibrational spectroscopy branch with unchanged rotational angular momentum quantum number. Differences between upper and lower rotational constants can resolve its transitions into closely spaced lines. Allowed lower-state values depend on the angular momenta of both states.

The rovibrational spectroscopy branch in which absorption raises the total rotational angular momentum quantum number by one. A label $R(J)$ conventionally specifies the lower-state value $J$.