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The heme is a planar chromophore, which makes it less sensitive to the mutual orientation of pump- and probe-beam polarization. It was shown elsewhere that, for planar chromophores, the theoretical limit for anisotropy is 0.1, whereas in the case of linear chromophores, it is 0.4. Rotational depolarization can be neglected because cyt c is a protein with the heme embedded in it and such a large object cannot rotate significantly on the time scale of tens of picoseconds (Ansari et al., Biophys. J. 1993, 64, 852-868). Our ultrafast polarization measurements confirm that there is no artifact introduced by using the crossed-polarization scheme.
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33645911331
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note
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The term missing amplitude is used to indicate the difference between the measured value of the transient absorption and the maximum possible value for 100% photolysis. In this case, it is calculated from the difference of the equilibrium absorptions of the photoproduct (MP-8) and reactant (AcMet-MP-8).
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85087227239
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note
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01 in absorption. The difference can be due to the different symmetry of the vibrational modes involved in the vibronic mixing of the ground and excited states or to preferential population and emission from specific vibrationally excited states of Q.
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33645921155
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Our photolysis calculations involve a comparison of the absorption cross sections of MbCO and cyt c at 401.5 nm. These values are taken from literature and bear some uncertainty.
-
Our photolysis calculations involve a comparison of the absorption cross sections of MbCO and cyt c at 401.5 nm. These values are taken from literature and bear some uncertainty.
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33
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33645918740
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We make an assumption that equilibrated photoproduct and MP-8 spectra are similar
-
We make an assumption that equilibrated photoproduct and MP-8 spectra are similar.
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0002052550
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Spiro, T. G., Ed.; Wiley-Interscience Publication: New York, Chapter 3
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Kitagawa T. In Biological Applications of Roman Spectroscopy; Spiro, T. G., Ed.; Wiley-Interscience Publication: New York, 1988; Chapter 3, pp 97-131.
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