Fine-structure effects in the antisymmetric stretching vibrational spectrum of FeH2 and FeD2

Author： Martini Heike Marian Christel M.

ISSN： 1362-3028

Source： Molecular Physics, Vol.94, Iss.5, 1998-08, pp. : 843-850

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Abstract

Relativistic ab initio calculations have been performed for the 5Delta, 5Pi, and 5Sigma+ electronic states of iron dihydride. We have determined potential energies along the antisymmetric stretching coordinate and coupling matrix elements including spin-orbit and rotational interactions. Vibrational excitation energies are in good agreement with recent gas phase experiments. We determine a first-order spin-orbit parameter of A SO,e = - 104.2cm-1 in the 5Delta ground state with the fine-structure splitting only slightly reduced by higher-order spinorbit interaction with the 5Pi and 5Sigma+ states. The higher-order effects are found to be mass dependent resulting in different spin-orbit splittings for FeH and FeD . The 5Pi and 5Sigma+ states are strongly coupled by both spin-orbit and rotational interaction rendering the definition of a first-order spin-orbit parameter for the 5Pi state meaningless. 2