Open AccessCO Vibration as a Probe of Ligand Dissociation and Transfer in Myoglobin
Author(s) -
Thomas Polack,
Jennifer P. Ogilvie,
Stefan Franzen,
Marten H. Vos,
M. Joffre,
JeanLouis Martin,
Antigoni Alexandrou
Publication year - 2004
Publication title -
physical review letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 3.688
H-Index - 673
eISSN - 1079-7114
pISSN - 0031-9007
DOI - 10.1103/physrevlett.93.018102
Subject(s) - myoglobin , femtosecond , oscillator strength , materials science , dissociation (chemistry) , photodissociation , atomic physics , vibration , heme , molecular physics , absorption spectroscopy , chemical physics , nuclear magnetic resonance , photochemistry , laser , chemistry , physics , optics , spectral line , astronomy , enzyme , organic chemistry , quantum mechanics
International audienceWe report femtosecond visible pump, midinfrared probe, spectrally integrated experiments resolving the dynamics of CO in myoglobin upon photodissociation. Our results show a progressive change in absorption strength of the CO vibrational transition during its transfer from the heme to the docking site, whereas the vibrational frequency change is faster than our time resolution. A phenomenological model gives good qualitative agreement with our data for a time constant of 400 fs for the change in oscillator strength. Density-functional calculations demonstrate that indeed vibrational frequency and absorption strength are not linearly coupled and that the absorption strength varies in a slower manner due to charge transfer from the heme iron to C
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