Radiationless decay from the ligand-to-metal charge-transfer state in the blue copper protein plastocyanin

The cysteine S(p π) → Cu 2+d x 2− y 2 ligand-to-metal charge-transfer (LMCT) state in plastocyanin exhibits a time-resolved pump-probe spectrum that has excited-state absorption and stimulated-emission components to the blue and red, respectively, of the absorption maximum. The LMCT state returns to...

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Bibliographic Details
Published in:Chemical physics letters 1997-08, Vol.275 (1), p.119-126
Main Authors: Edington, Maurice D., Diffey, William M., Doria, William J., Riter, Ruth E., Beck, Warren F.
Format: Article
Language:English
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Summary:The cysteine S(p π) → Cu 2+d x 2− y 2 ligand-to-metal charge-transfer (LMCT) state in plastocyanin exhibits a time-resolved pump-probe spectrum that has excited-state absorption and stimulated-emission components to the blue and red, respectively, of the absorption maximum. The LMCT state returns to the ground state by populating the d xz+ yz → d x 2− y 2 ligand-field (LF) state. The lack of hole-burned features in the time-resolved spectra implies the presence of intramolecular vibrational redistribution and/or protein-matrix solvation dynamics on a time scale that is shorter than the 125 fs lifetime of the LMCT state.
ISSN:0009-2614
1873-4448
DOI:10.1016/S0009-2614(97)00738-0