Abstract
The polarization properties of electric quadrupole contributions to molecular electronic transitions are examined theoretically. Possible manifestations of these electric quadrupole contributions in various types of polarized absorption and emission spectra are considered in detail. The types of polarized spectra considered are circular dichroism (CD), linear dichroism (LD), circularly polarized luminescence (CPL), linearly polarized luminescence (LPL), magnetic circular dichroism (MCD), magnetic linear dichroism (MLD), magnetic circularly polarized luminescence (MCPL), and magnetic linearly polarized luminescence (MLPL). In emission the possible effects of photoselection and reorientational relaxation are investigated. Calculations are presented for the A2g↔T1g transitions of octahedral (Oh) systems and for the Σ+g↔Πu, Πg, and Δg transitions of homonuclear diatomic molecules (D∞h) under a variety of conditions. The identification and characterization of pure electric quadrupole (electronic) transitions using polarized absorption/emission spectroscopy are discussed.
Published Version
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