Vibrational equilibration in absorption difference spectra of chlorophyll a.

Abstract:

:We describe Franck-Condon simulations of vibrational cooling effects on absorption difference spectra in chlorophyll a (Chl a). The relative contributions of vibrational equilibration in the electronic ground and excited states depend on the pump and probe wavelengths. For Franck-Condon-active vibrational modes exhibiting small Huang-Rhys factors (S < 0.1, characteristic in Chl a pigments), vibrational thermalization causes essentially no spectral changes when the origin band is excited. Significant spectral evolution does occur for S < 0.1 when the 0-1 and 1.0 (hot) vibronic bands are excited. However, vibrational equilibration in these cases causes no spectral shifting in the empirical photobleaching/stimulated emission band maximum. This result bears on the interpretation of time-resolved absorption difference spectra of Chl a-containing antennae such as the Chl a/b light-harvesting peripheral antenna of photosystem II.

journal_name

Biophys J

journal_title

Biophysical journal

authors

Struve WS

doi

10.1016/S0006-3495(95)80145-1

subject

Has Abstract

pub_date

1995-12-01 00:00:00

pages

2739-44

issue

6

eissn

0006-3495

issn

1542-0086

pii

S0006-3495(95)80145-1

journal_volume

69

pub_type

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