Ground State Characteristics and Optical Spectra of Ce and Eu Octaethyl Bisporphyrinate Double Deckers.
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
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1995
- Accession Number
- ADA303907
Entities
People
- Guillermina L. Estiu
- Michael C. Zerner
- Notker Roesch
Organizations
- University of Florida