Remembering Gerald J. Small (1941–2004), who tackled everything in life with an intense and enviable passion

Insight into the Electronic Structure of the CP47 Antenna Protein Complex of Photosystem II: Hole Burning and Fluorescence Study

“…The hole-burning apparatus used is described in. refs and − . Briefly, absorption and HB spectra were recorded with a Bruker HR125 Fourier transform spectrometer at a resolution of either 4 cm −1 or 0.5 cm −1 .…”

“…The same stabilized ring dye laser pumped by the Ar + ion laser (see above) was used to generate the FLN and delta-FLN (ΔFLN) spectra. The Huang−Rhys factor ( S ) for phonon sideband was obtained by SHB. ,− The shape of the phonon sideband was obtained by fitting the pseudophonon hole in the low-fluence 693 nm SHB spectrum and was tested by comparing the calculated ΔFLN spectrum (using the SHB sideband) with the phonon sideband of the experimental 697 nm ΔFLN spectrum . All resonant FLN and ΔFLN spectra were recorded with a resolution of 1.5 cm −1 using a PI Acton SpectraPro 2300i triple grating monochromator equipped with the Spec-10 CCD (back illuminated) camera.…”

Site Selective and Single Complex Laser-Based Spectroscopies: A Window on Excited State Electronic Structure, Excitation Energy Transfer, and Electron–Phonon Coupling of Selected Photosynthetic Complexes

“…The successes of SHB spectroscopies (nonphotochemical, photochemical, triplet population bottleneck) ,, demonstrated over the years that these frequency domain techniques provide a lot of insight into the S 1 (Q y )-excited state electronic structure, EET, and electron transfer (ET) dynamics of protein–Chl complexes at low temperatures. A number of applications have been described in ref , while the basic principles of various high resolution spectroscopies have been explained in numerous books, , reviews, ,, and book chapters. , The advantages of SHB ,,,− in photosynthesis research stem from its ability to circumvent the inhomogeneous broadeningthe static Γ inh contribution to the widths of the S 0 →S 1 absorption bands of Chl molecules and other cofactors. Γ inh is a manifestation of the glasslike structural heterogeneity of proteins. ,,, The parameters provided by SHB ,,,,− are listed below and further discussed in subsequent sections.…”

“…A number of applications have been described in ref , while the basic principles of various high resolution spectroscopies have been explained in numerous books, , reviews, ,, and book chapters. , The advantages of SHB ,,,− in photosynthesis research stem from its ability to circumvent the inhomogeneous broadeningthe static Γ inh contribution to the widths of the S 0 →S 1 absorption bands of Chl molecules and other cofactors. Γ inh is a manifestation of the glasslike structural heterogeneity of proteins. ,,, The parameters provided by SHB ,,,,− are listed below and further discussed in subsequent sections. These parameters are essential for understanding EET, since they often determine the homogeneous spectral density in the nonadiabatic transfer rate expression (eq ) .…”

“…This broadening obscures the information on the dynamics of the system. Several (low-temperature) laser-based techniques that can overcome the inhomogeneous broadening and access the homogeneous (natural) line width have been developed. − This review provides a brief description and a critical account of site-selective spectroscopies, i.e., spectral hole-burning (SHB) − and fluorescence line-narrowing (FLN), − as well as their applications in the area of photosynthesis research (for recent reviews see refs , ). It was Kharlamov and co-workers and Gorokhovskii and co-workers who first observed the nonphotochemical hole-burning (NPHB), as it later came to be called.…”