Accession Number : ADA303907

Title :   Ground State Characteristics and Optical Spectra of Ce and Eu Octaethyl Bisporphyrinate Double Deckers.

Descriptive Note : Interim rept.,

Corporate Author : FLORIDA UNIV GAINESVILLE DEPT OF CHEMISTRY

Personal Author(s) : Estiu, Guillermina L. ; Roesch, Notker ; Zerner, Michael C.

PDF Url : ADA303907

Report Date : 1995

Pagination or Media Count : 42

Abstract : The ground state electronic structure and optical spectra of Ce(III), Ce(IV) and Eu(III) octaethyl bisporphyrin dimers (double deckers) are examined using the Intermediate Neglect of Differential Overlap (INDO/S) model and multireference configuration interaction (MRCI). The low energy electronic excited states of the dimers are interpreted in terms of their monomer contributions, and the charge transfer and excitonic character of the transitions are analyzed. Particular attention is focused on the nature of the near infrared band (NIR) that characterizes the spectra of the electron deficient bisporphyrin dimers, justifying its shift to higher energy as the ionic radii of the central ion decreases, and relating its broadness to the contribution of closely spaced electronic transitions that become allowed through vibronic coupling. The influence of an electric perturbation on the dimeric Ce(IV) and Eu(III) structures is used to explain their conductivity. The results are compared to those derived from resonant Raman spectroscopy, which show the importance of the vibrational fine structure in the assignment of the NIR band. jg p4

Descriptors :   *OPTICAL PROPERTIES, *SPECTRA, *CERIUM, *GROUND STATE, *EUROPIUM, COUPLING(INTERACTION), ELECTRONICS, IONS, VIBRATION, CONDUCTIVITY, QUANTUM THEORY, RAMAN SPECTROSCOPY, ENERGY, SHIFTING, RESONANCE, CHARGE TRANSFER, VISIBLE SPECTRA, ELECTRIC POWER, PERTURBATIONS, OVERLAP, ELECTRON TRANSITIONS, NEAR INFRARED RADIATION, ETHYL RADICALS, DIMERS, EXCITONS.

Subject Categories : Polymer Chemistry
      Inorganic Chemistry
      Organic Chemistry
      Atomic and Molecular Physics and Spectroscopy

Distribution Statement : APPROVED FOR PUBLIC RELEASE