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Real chemical bonds can stretch as molecular rotation increases. The resulting larger moment of inertia lowers the energy eigenvalues relative to a rigid rotor. Within one vibrational quantum state, a leading effective correction isBoth $B_v$ and $D_v$ are in frequency units here; $v$ labels the vibrational quantum state. For positive $D_v$, the adjacent-line spacing becomesso the departures grow with $J$. Molecular vibration also changes the effective rotational constant: even the lowest vibrational quantum state does not have motionless atomic nuclei.^[ref]

The quartic correction is a limited expansion, not a model to extrapolate to arbitrary $J$. It is small relative to the rigid contribution only while $(D_v/B_v)J(J+1)\ll 1$; eventually higher terms, changed internal motion, or chemical bond breaking matter. In the synthetic plot, the largest upper-state label is $J=5$, giving a stipulated correction ratio of $0.03$. No universal maximum valid $J$ follows without a particular molecule and precision target.

The quantum numbers also have limits of meaning. Here $J$ describes spin-free rotation. In a molecule with electronic spin, rotation alone is commonly labelled $N$, while $J$ includes electronic angular momentum; including nuclear spin introduces additional total-angular momentum labels and resolved splittings. An applied electric field can mix different field-free $J$ states through the Stark effect. For identical atomic nuclei, the Pauli exclusion principle can restrict combinations of rotational and nuclear-spin states. The simple $2J+1$ degeneracy and every-integer-$J$ ladder therefore describe the stated idealization, not all observed sublevels.^[ref]

Changing an isotope changes a mass and therefore the moment of inertia. If the bond length is held fixed, $B\propto 1/\mu$ and every corresponding transition shifts by the same fractional amount. This leading inverse-reduced mass scaling is also used in the more complete diatomic formulation.^[ref]

For a deliberately stipulated carbon monoxide example, take $m_{12}=12u$, $m_{13}=13u$, $m_{16}=16u$, $u=1.66053906660\times 10^{-27}\mathrm{kg}$, $r=1.13\times 10^{-10}\mathrm{m}$ for both isotopic forms, and $h=6.62607015\times 10^{-34}\mathrm{J}\mathrm{s}$. The integer masses are simplifying inputs, not accurate isotopic atomic masses; the shared bond length is an imposed model assumption. Calculation givesIn particular,The heavier form's calculated $J=0\to 1$ line is $110.363\mathrm{GHz}$ rather than $115.438\mathrm{GHz}$, a decrease of about $4.396\%$. These are model predictions from the stated inputs, not published measured frequencies. An isotope changes the spacing as well as the first line; the shift is not a fixed additive offset for the whole spectrum.

A rotational spectral line assignment associates a measured spectral line with a molecule, an internal quantum state, and an initial and final set of quantum numbers. For the spin-free linear rigid rotor, absorption is labelled $J\to J+1$. A regularly spaced group suggests a candidate rotational constant, but the lowest line inside a scanned band need not be $0\to 1$. Several molecules can contribute to the same spectrum, and an apparent missing member can lie outside the band or below the detection threshold.

First determine line centers and their uncertainties from the instrument's readout, accounting for resolved Doppler shifts or hyperfine structure rather than treating every peak as a separate rotational transition. Then propose integer assignments, fit a rotational Hamiltonian, and predict additional spectral lines. For a weakly distorted linear molecule within one vibrational quantum state, the centrifugal distortion model gives the useful diagnosticHere $B,D,{\nu }_m$ are all frequencies in $\mathrm{Hz}$. Correct assignments make the second expression a straight line against $m^2$, with intercept $B$ and slope $-2D$. This follows by division of the transition formula; no additional model of molecular geometry is required. A direct weighted least squares fit of ${\nu }_m$ to $2Bm-4D{m}^3$ uses the measured uncertainties. If instead the transformed values are fitted, their uncertainties must also be divided by $2m$.^[ref]

For an original example, stipulate $B=5.000000\mathrm{GHz}$ and $D=2.000\mathrm{kHz}$, and suppose a scan covers $38$–$72\mathrm{GHz}$. The model places four consecutive transitions at $39.999488$, $49.999000$, $59.998272$, and $69.997256\mathrm{GHz}$. Their assignments are $m=4,5,6,7$, hence $J=3,4,5,6$. An extra stipulated line at $53.2\mathrm{GHz}$ is unrelated to this series. All these frequencies are calculated example inputs, not measured OCS data.

At $m=4$ and $m=7$, the transformed values are $4999.936$ and $4999.804\mathrm{MHz}$. Their straight line has slope $(4999.804-4999.936)/(49-16)=-0.004\mathrm{MHz}$, recovering $D=0.002\mathrm{MHz}$ and $B=5000\mathrm{MHz}$. Both intermediate transitions satisfy the same line exactly. Merely relabelling the first visible transition $0\to 1$ fails this diagnostic. The model predicts a withheld $7\to 8$ transition at $79.995904\mathrm{GHz}$: an additional measurement there would test the assignment rather than merely refit the original four lines.

An assignment earns confidence when several independently observed spectral lines, including lines outside the fitted interval, agree within uncertainty and expected strong accessible lines are present. Inspect the residual of an inverse problem for each line against $J$: systematic curvature can signal inadequate centrifugal distortion, whereas isolated discrepancies suggest a blend or wrong assignment. Comparing a known sample, a blank, and an isotope shift of a linear rotor supplies different checks. These are general inference controls; the actual reported controls of the NIST trace-gas FTMW validation experiment are described separately. One isolated match or one fitted rotational constant alone cannot certify molecular identity.