作者: Robert L. Ake , Martin Gouterman
DOI: 10.1007/BF00526463
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摘要: The normal triplet state of closed shell metal porphyrins becomes a “tripdoublet” and quartet in systems with one unpaired d electron. Exchange integrals between porphyrin π-electrons give intensity to the tripdoublet set tripdoublet-quartet energy gap. These are evaluated theoretically giving radiative lifetimes 26 1450 μsec gaps range 156 639 cm−1 for metals skeletons considered. Spinorbit coupling similarly gives causes zero field splitting dependent on parameter Z which has value 0.7, 3.5, 20.4, 21.6 Zn (triplet), Cu, Co VO complexes. Theory predicts that ratio 0−1 0−0 bands will be very low but stronger quartet. Existing experimental evidence shows luminescence comes from both states, their relative importance varying metal, skeleton, temperature.