[Physics] Why doesn’t the ${\rm H}_2$ molecule have a permanent dipole while the neutral ${\rm H}\,{\rm\small I}$ has one

astronomyhydrogenmoleculesradio frequencyspectroscopy

According to the National Radio Astronomy Observatory, the $21\,{\rm cm}$ line of hydrogen can be emitted by the neutral hydrogen atom due to the magnetic interaction between the spins of the proton and electron. However, it says the hydrogen molecule ${\rm H}_2$ does not posses a permanent dipole, and thus does not emit a spectral line at radio frequencies. Why is that the interaction between the spins of the proton and electrons no longer manifests itself when we are talking about the ${\rm H}_2$ molecule?

Best Answer

$H_2$ contains 2 electrons in the same ground-state orbital; by Pauli exclusion, one must be spin-up and the other must be spin-down. The 21cm line is generated in a normal hydrogen atom when an electron's spin flips from being aligned with the proton to being anti-aligned with the proton. In $H_2$, an electron's spin cannot flip because it would then be occupying the same state as the other electron. Even if it could, the differing shape of the orbital would produce a line at a significantly different wavelength than 21cm.

The two protons, since they're not in the same orbital, can exhibit a similar type of transition as the 21cm line (i.e. proton spin flips from aligned to anti-aligned), but since the protons are highly localized, massive, and far apart, any spin-spin coupling between them is insignificant. Indeed, when measured, this transition has a frequency of just 72 kHz, corresponding to a wavelength of over 4 km.

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