The high-field rotational Zeeman effect has been observed in several rotational transitions of the (010) vibrational state in OCS and HCN. The magnetic-field splittings are in agreement with a simple first-order energy expression which is derived to hold for the Zeeman energies of rotation-vibrational states of a linear polyatomic molecule showing rotational l-type-doubling. In this way, the presence of intrinsic magnetic moments in the π-vibrational states has been shown experimentally. The g-values along the molecular axis are gǁ (010)= +0.061 ± 0.002 for OCS and gǁ (010)=±0.38 ± 0.06 for HCN. No magnetic anisotropics could be detected within the plane perpendicular to the molecular axis. The other parameters measured are g⊥(010)= -0.0285 ± 0.0006 and (χ⊥ - χǁ)(010) = (8.0 ±1.0) × 10-6 erg/G2mole for OCS and gǁ (010) = ∓ 0.100 ±0.001 for HCN which "can be considered an approximate value for the vibrational ground-state. Either the upper or the lower signs hold for the g-values of HCN. The intrinsic g-values, gǁ (010) , are discussed in terms of nuclear and electronic contributions. A quantity measuring the slip of a rotating nuclear framework within its electronic environment is defined and also discussed.
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Hüttner et al. (1970) studied this question.