A tabulated electronegativity is useful because it compresses many comparisons, but one number per chemical element suppresses chemical context. Changing the bonded partners, bond length or electron configuration changes the conditions under which a chemical atom attracts electron density. The bond-dissociation energy can change for reasons beyond bond polarization, so attributing every extra unit of energy solely to an electronegativity difference is an approximation.[ref]
An oxidation state labels a formal allocation of Electrons; it is not a measured partial atomic charge. State-sensitive electronegativity models may give different values for different oxidation states or electron configurations, while a simple chemical element table intentionally provides a common comparison convention. Likewise, replacing an isolated chemical atom by a site in an ionic crystal introduces a surrounding electric field and many neighbours. Applying the same tabulated electronegativity without adjustment becomes an additional assumption.[ref]
For the ground-state Mulliken scale, the state dependence is visible directly in the formula. Replacing by replaces with as the removal cost, and replaces with as the attachment release. These are different ionization energies and electron affinities. This isolated-ion arithmetic does not claim that a bonded chemical atom with the same formal oxidation state is an isolated ion. In a molecule, the actual electron density and dipole evidence for bond polarization supply complementary information about that environment.
The apparatus and dipole inference are described under dipole evidence for bond polarization. The rigid rotor supplies a general starting model for rotational quantum states; rotational spectroscopy measures their transition frequencies, while molecular beam electric resonance can select and analyze states through their Stark effects.