THE ORIGIN OF STARK SPLITTINGS IN MOLECULAR CRYSTAL SPECTRA
Publisher:
Ohio State UniversityAbstract:
It has been suggested that the Stark splitting of spectral lines of molecular crystals in an external electric field can be attributed to a molecular electric dipole moment $change^{1}$ interacting with the local electric field. An anisotropic Lorentz field approximation was used to obtain the local field from the macroscopic $field.^{1,2}$. Other $interactions^{3}$ in the crystal can contribute significantly to the Stark splitting, and many of these have been ignored in previous analyses of such Stark effects. By explicitly including, in a self-consistent way, the many contributions that can arise from guest and host dipole-dipole and dipole-electric field interactions, an improved analysis of the Stark splitting in the spectra of a polar impurity isolated in a nonpolar host crystal is obtained in closed $form,^{4}$ within the context of the point dipole approximation. This analysis results in a second rank tensor that couples the molecular dipole moment change to the macroscopic electric field. This tensor will be compared with that obtained from the Lorentz local field analysis.
Description:
$^{1}$R. M. Hochstrasser, Accounts Chem. Res, 6, 263 (1973). $^{2}$R. M. Hochstrasser and L. J. Noe, J. Chem. Phys. 48, 514 (1968). $^{3}$D. M. Hanson and F. P. Chen, Eleventh European Congress on Molecular Spectroscopy, Tallinn, Estonia, USSR, 1973, Sec. B5, Abstract 173.""
Author Institution: Department of Chemistry, State University of New York; Department of Physics, State University of New York
Author Institution: Department of Chemistry, State University of New York; Department of Physics, State University of New York
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