No abstract

Electron-phonon and electron-vibrational coupling strengths of a weakly (excitonically) coupled chlorophyll a S1-->S0 transition of the CP29 antenna complex of plant photosystem II were studied by difference fluorescence-line-narrowing spectroscopy at 4.5 K. A strong, almost linear increase of the electron-phonon coupling strength toward longer wavelengths was observed, with Huang-Rhys factors Sph increasing from 0.41+/-0.05 at 680 nm to about 0.66+/-0.07 at 688 nm. The former and latter wavelengths are located close to the peak and on the red edge of the inhomogeneous site distribution function, respectively. The experimentally obtained wavelength dependence of Sph may originate either from an alteration of the electron-phonon coupling strength by the local environment of the fluorescing chromophore and/or from the presence of two isoforms of CP29, which are characterized by different coupling strengths to the protein environment. The one-phonon profile peaks at omegam=22 cm(-1) and is described by an asymmetric function composed of a Gaussian low-energy wing and a Lorentzian high-energy tail with half-widths at half-maximum of 10+/-1 and 60+/-10 cm(-1), respectively. Thirty-nine individual vibrational modes between 90 and 1665 cm(-1) were resolved, and their Huang-Rhys factors were determined, which fall in the range between 0.0004 and 0.032. The broad feature present in the overlap region of phonon and vibrational modes at about 90 cm(-1) is characterized by S=0.048. An integral value of vibrational coupling strengths Svib=0.36+/-0.05 was determined, which is similar to that observed earlier for the trimeric LHC II complex.

Difference fluorescence line-narrowing spectroscopy at 4.5 K was employed to investigate electron-phonon and electron-vibrational coupling strengths of the lower exciton level of water-soluble chlorophyll-binding protein (WSCP) from cauliflower reconstituted with chlorophyll a or chlorophyll b, respectively. The electron-phonon coupling is found to be moderate with integral Huang-Rhys factors S in the order of 0.81-0.85. A weak dependence of S on excitation wavelength within the inhomogeneously broadened fluorescence origin band is attributed to a sizable contribution of nonresonant excitation that varies with excitation wavelength. The strongly asymmetric and highly structured one-phonon profile is characterized by a peak phonon frequency (ω(m)) of ~24 cm(-1) and further discernible peaks at 48 and 88 cm(-1), respectively. A structural assignment of this unusual one-phonon profile is proposed. As will be shown in the accompanying paper (part II) (DOI 10.1021/jp111457t), the parameters of electron-phonon coupling readily account for shape and position of the fluorescence origin bands at 666.1 and 683.8 nm for chlorophyll b- and chlorophyll a-WSCP, respectively. A rich structure of S(1)→S(0) vibrational frequencies was resolved in the wavenumber range between 180 and 1665 cm(-1) for both chlorophyll a- and chlorophyll b-WSCP. The corresponding individual Huang-Rhys factors fall in the range between 0.0011 and 0.0500. To the best of our knowledge, this is the first report of S-factors for vibrational modes of chlorophyll b. Most remarkable is the presence of two additional modes at 228 and 327 cm(-1) compared with the vibrational spectrum of chlorophyll in solution. The additional modes can most likely be attributed to H-bond formation in the vicinity of the chlorophyll molecule bound by WSCP.

The absorption and fluorescence emission spectra of chlorophyll a in different organic solvents where the central Mg atom is either penta- or hexacoordinated have been studied using conventional and selective spectroscopy methods at ambient and cryogenic temperatures. A breakdown of the basic model mirror-symmetry rule in relation to the lowest-energy Q(y) transitions was observed due to Franck-Condon and Hertzberg-Teller interactions. Detailed vibrational structure in the ground electronic state, virtually independent of the Mg coordination state, was revealed by hole-burning fluorescence line-narrowing technique. The total Huang-Rhys factor associated with the linear vibronic coupling strength of the solvent collective vibrations and the local chlorophyll a intramolecular vibrations is equal to 0.53+/-0.07 in fluorescence and to 0.39+/-0.05 in absorption. The electron-phonon coupling part was also found to depend on the excitation wavelength within the inhomogeneously broadened absorption origin band, its average value being S(ph) approximately = 0.38. All these numbers qualify for the weak vibronic coupling. A comparison of the conjugate Q(y) absorption and fluorescence emission spectra as well as the temperature dependence of the absorption spectra allowed unambiguous locating of the still controversial Q(x) absorption band position for penta- and hexacoordinated chlorophyll a species. The basic experimental findings have been qualitatively supported by semiempirical quantum chemical calculations.