Accession Number : ADA293669

Title :   A Theoretical Treatment of the Absorption and Emission Properties of Cu(II) Porphyrin

Descriptive Note : Interim rept.,

Corporate Author : FLORIDA UNIV GAINESVILLE DEPT OF CHEMISTRY

Personal Author(s) : Stavrev, Krassimir ; Zerner, Michael C.

PDF Url : ADA293669

Report Date : 18 APR 1995

Pagination or Media Count : 21

Abstract : We examine the electronic spectrum of Cu(II) Porphyrin using the Intermediate Neglect of Differential Overlap (INDO) model that has been specifically parametrized for spectroscopy at the configuration interaction level of theory. The isolated molecule is predicted to have a trip-doublet absorption, corresponding to porphyrin triplets, at about 9,000/cm and 13,900/cm.The Q band is calculated at 15,900/cm, in good accord with experimental values. We predict a normal emission in this case, as is observed. We find that chelating in the fifth position with a strong ligand such as pyridine leads to a state in energy below the Q band that is mostly d(z squared)>d(x squared-y squared) but with appreciable a2u(Pi)>d(x squared-y squared) character. We postulate that it is the presence of this state that quenches the emission when Cu(II) porphyrins are complexed with strong fifth or fifth and sixth position ligands. jg

Descriptors :   *EMISSION, *COPPER, *ABSORPTION, *PORPHYRINS, ELECTRONICS, SPECTROSCOPY, QUANTUM CHEMISTRY, INTERACTIONS, MOLECULES, ISOLATION, SPECTRA, CONFIGURATIONS, LIGANDS, PYRIDINES, CHELATE COMPOUNDS, Q BAND.

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

Distribution Statement : APPROVED FOR PUBLIC RELEASE