5 - Quantum Mechanical Analysis of Single-Photon Electric Dipole Resonances for Diatomic Molecules

Summary

The interaction of electromagnetic radiation with single-photon resonances in diatomic molecules is discussed in this chapter. The properties of the electric dipole moment of the molecule are determined primarily by the electron cloud that binds the two nuclei together, and these properties can be understood by considering a reference frame fixed to the molecule. However, the response of the molecule must be averaged over all possible orientations of the molecule in the laboratory frame. Using irreducible spherical tensors greatly simplifies the orientation averaging of the molecular response. The Born–Oppenheimer approximation is invoked to initially account for the effect of the electronic, vibrational, and rotational modes of the molecule. Corrections are applied to account for the coupling and interactions of the different modes, including Herman–Wallis effects. Tables of rotational line strengths are presented for singlet, doublet, and triplet electronic transitions. These tables incorporate the use of Hund’s case (a) basis state wavefunctions for increased insight into radiative interactions for levels intermediate between Hund’s cases (a) and (b).