ISSN:
0020-7608
Schlagwort(e):
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Ab initio methods have been used to calculate the ground and excited states of “normal” and “hyper” porphyrins. Perturbation theory and CI methods were used to determine differential ground and excited-state correlation effects for [Pv(P)F2]+ and [PIII(P)]+. A comparison is made to the INDO/S/CI predicted wavefunctions and spectra and to the experimental spectra of closely related molecules. The “hyper” [PIII(P)]+ calculations show some very low energy electronic transitions which provide an explanation for an anomalous “red” band in the spectrum and for the lack of fluorescence. Ab initio calculations also predict that (1) the lowest energy 1A1 state is a two-configuration wavefunction which can be described as a diradical, (2) the two lowest-energy singlet excited states are double excitations from the closed shell SCF configuration, and (3) a 3B2 state is very close in energy to the lowest 1A1 state.
Zusätzliches Material:
9 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/qua.560260210
