Modeling of fluorescence line-narrowed spectra in weakly coupled dimers in the presence of excitation energy transfer.

This work describes simple analytical formulas to describe the fluorescence line-narrowed (FLN) spectra of weakly coupled chromophores in the presence of excitation energy transfer (EET). Modeling studies for dimer systems (assuming low fluence and weak coupling) show that the FLN spectra (including absorption and emission spectra) calculated for various dimers using our model are in good agreement with spectra calculated by: (i) the simple convolution method and (ii) the more rigorous treatment using the Redfield approach [T. Renger and R. A. Marcus, J. Chem. Phys. 116, 9997 (2002)]. The calculated FLN spectra in the presence of EET of all three approaches are very similar. We argue that our approach provides a simplified and computationally more efficient description of FLN spectra in the presence of EET. This method also has been applied to FLN spectra obtained for the CP47 antenna complex of Photosystem II reported by Neupane et al. [J. Am. Chem. Soc. 132, 4214 (2010)], which indicated the presence of uncorrelated EET between pigments contributing to the two lowest energy (overlapping) exciton states, each mostly localized on a single chromophore. Calculated and experimental FLN spectra for CP47 complex show very good qualitative agreement.

Charge-transfer character of the low-energy Chl a Q(y) absorption band in aggregated light harvesting complexes II.

One of the key functions of the major light harvesting complex II (LHCII) of higher plants is to protect Photosystem II from photodamage at excessive light conditions in a process called "non-photochemical quenching" (NPQ). Using hole-burning (HB) spectroscopy, we investigated the nature of the low-energy absorption band in aggregated LHCII complexes - which are highly quenched and have been established as a good in vitro model for NPQ. Nonresonant holes reveal that the lowest energy state (located near 683.3 nm) is red-shifted by ~4 nm and significantly broader (by a factor of 4) as compared to nonaggregated trimeric LHCII. Resonant holes burned in the low-energy wing of the absorption spectrum (685-710 nm) showed a high electron-phonon (el-ph) coupling strength with a Huang-Rhys factor S of 3-4. This finding combined with the very low HB efficiency in the long-wavelength absorption tail is consistent with a dominant charge-transfer (CT) character of the lowest energy transition(s) in aggregated LHCII. The value of S decreases at shorter wavelengths (<685 nm), in agreement with previous studies (J. Pieper et al., J. Phys. Chem. B 1999, 103, 2422-2428), proving that the low-energy excitonic state is strongly mixed with the CT states. Our findings support the mechanistic model in which Chl-Chl CT states formed in aggregated LHCII are intermediates in the efficient excited state quenching process (M. G. Müller et al., Chem. Phys. Chem. 2010, 11, 1289-1296; Y. Miloslavina et al., FEBS Lett. 2008, 582, 3625-3631).

Modeling of optical spectra of the light-harvesting CP29 antenna complex of photosystem II--part II.

Until recently, it was believed that the CP29 protein from higher plant photosystem II (PSII) contains 8 chlorophylls (Chl's) per complex (Ahn et al. Science 2008, 320, 794-797; Bassi et al. Proc. Natl. Acad. Sci. U.S.A. 1999, 96, 10056-10061) in contrast to the 13 Chl's revealed by the recent X-ray structure (Pan et al. Nat. Struct. Mol. Biol. 2011, 18, 309-315). This disagreement presents a constraint on the interpretation of the underlying electronic structure of this complex. To shed more light on the interpretation of various experimental optical spectra discussed in the accompanying paper (part I, DOI 10.1021/jp4004328 ), we report here calculated low-temperature (5 K) absorption, fluorescence, hole-burned (HB), and 300 K circular dichroism (CD) spectra for CP29 complexes with a different number of pigments. We focus on excitonic structure and the nature of the low-energy state using modeling based on the X-ray structure of CP29 and Redfield theory. We show that the lowest energy state is mostly contributed to by a612, a611, and a615 Chl's. We suggest that in the previously studied CP29 complexes from spinach (Pieper et al. Photochem. Photobiol.2000, 71, 574-589) two Chl's could have been lost during the preparation/purification procedure, but it is unlikely that the spinach CP29 protein contains only eight Chl's, as suggested by the sequence homology-based study (Bassi et al. Proc. Natl. Acad. Sci. U.S.A.1999, 96, 10056-10061). The likely Chl's missing in wild-type (WT) CP29 complexes studied previously (Pieper et al. Photochem. Photobiol. 2000, 71, 574-589) include a615 and b607. This is why the nonresonant HB spectra shown in that reference were ~1 nm blue-shifted with the low-energy state mostly localized on about one Chl a (i.e., a612) molecule. Pigment composition of CP29 is discussed in the context of light-harvesting and excitation energy transfer.

Spectroscopic study of the light-harvesting CP29 antenna complex of photosystem II--part I.

Recent structural data revealed that the CP29 protein of higher plant photosystem II (PSII) contains 13 chlorophylls (Chl's) per complex (Pan et al. Nat. Struct. Mol. Biol. 2011, 18, 309), i.e., five Chl's more than in the predicted CP29 homology-based structure model (Bassi et al. Proc. Natl. Acad. Sci. U.S.A. 1999, 96, 10056). This lack of consensus presents a constraint on the interpretation of CP29 optical spectra and their underlying electronic structure. To address this problem, we present new low-temperature (5 K) absorption, fluorescence, and hole-burned (HB) spectra for CP29 proteins from spinach, which are compared with the previously reported data. We focus on excitation energy transfer (EET) and the nature of the lowest-energy state(s). We argue that CP29 proteins previously studied by HB spectroscopy lacked at least one Chl a molecule (i.e., a615 or a611), which along with Chl a612 contribute to the lowest energy state in more intact CP29, and one Chl b (most likely b607). This is why the low-energy state and fluorescence maxima reported by Pieper et al. (Photochem. Photobiol.2000, 71, 574) were blue-shifted by ~1 nm, the low-energy state appeared to be highly localized on a single Chl a molecule, and the position of the low-energy state was independent of burning fluence. In contrast, the position of the nonresonant HB spectrum shifts blue with increasing fluence in intact CP29, as this state is strongly contributed to by several pigments (i.e., a611, a612, a615, and a610). Zero-phonon hole widths obtained for the Chl b band at 638.5 nm (5 K) revealed two independent Chl b → Chl a EET times, i.e., 4 ± 0.5 and 0.4 ± 0.1 ps. The latter value is a factor of 2 faster than previously observed by HB spectroscopy and very similar to the one observed by Gradinaru et al. (J. Phys. Chem. B 2000, 104, 9330) in pump-probe experiments. EET time from 650 nm Chl b → Chl a and downward EET from Chl(s) a state(s) at 665 nm occurs in 4.9 ± 0.7 ps. These findings provide important constraints for excitonic calculations that are discussed in the accompanying paper (part II, DOI 10.1021/jp4004278 ).

On the shape of the phonon spectral density in photosynthetic complexes.

We provide a critical assessment of typical phonon spectral densities, J(ω), used to describe linear and nonlinear optical spectra in photosynthetic complexes. Evaluation is based on a more careful comparison to experiment than has been provided in the past. J(ω) describes the frequency-dependent coupling of the system to the bath and is an important component in calculations of excitation energy transfer times. On the basis of the shape of experimental J(ω) obtained for several photosynthetic complexes, we argue that the shape of J(ω) strongly depends on the pigment-protein complex. We show that many densities (especially the Drude-Lorentz/constant damping Brownian oscillator) display qualitatively wrong behavior when compared to experiment. Because of divergence of J(ω) at zero frequency, the Brownian oscillator cannot fit a single-site spectrum correctly. It is proposed that a log-normal distribution can be used to fit experimental data and exhibits desired attributes for a physically meaningful phonon J(ω), in contrast to several commonly used spectral densities which exhibit low-frequency behavior in qualitative disagreement with experiment. We anticipate that the log-normal J(ω) function proposed in this work will be further tested in theoretical modeling of both time- and frequency-domain data.

Spectroscopic study of the CP43' complex and the PSI-CP43' supercomplex of the cyanobacterium Synechocystis PCC 6803.

The PSI-CP43' supercomplex of the cyanobacterium Synechocystis PCC 6803, grown under iron-starvation conditions, consists of a trimeric core Photosystem I (PSI) complex and an outer ring of 18 CP43' light-harvesting complexes. We have investigated the electronic structure and excitation energy transfer (EET) pathways within the CP43' (also known as the isiA gene product) ring using low-temperature absorption, fluorescence, fluorescence excitation, and hole-burning (HB) spectroscopies. Analysis of the absorption spectra of PSI, CP43', and PSI-CP43' complexes suggests that there are 13 chlorophylls (Chls) per CP43' monomer, i.e., a number that was observed in the CP43 complex of Photosystem II (PSII) (Umena, Y. et al. Nature 2011, 473, 55-60). This is in contrast with the recent modeling studies of Zhang et al. (Biochim. Biophys. Acta 2010, 1797, 457-465), which suggested that IsiA likely contains 15 Chls. Modeling studies of various optical spectra of the CP43' ring using the uncorrelated EET model (Zazubovich, V.; Jankowiak, R. J. Lumin. 2007, 127, 245-250) suggest that CP43' monomers (in analogy to the CP43 complexes of the PSII core) also possess two quasi-degenerate low-energy states, A' and B'. The site distribution functions of states A' and B' maxima/full width at half-maximum (fwhm) are at 684 nm/180 cm(-1) and 683 nm/80 cm(-1), respectively. Our analysis shows that pigments mostly contributing to the lowest-energy A' and B' states must be located on the side of the CP43' complex facing the PSI core, a finding that contradicts the model of Zhang et al. but is in agreement with the model suggested by Nield et al. (Biochemistry2003, 42, 3180-3188). We demonstrate that the A'-A' and B'-B' EET between different monomers is possible, though with a slower rate than intramonomer A'-B' and/or B'-A' energy transfer.

Calibration of electron spectrometer resolution in attosecond streak camera.

We report a new method for determining the energy resolution of time-of-flight spectrometers for detecting photoelectrons produced with attosecond XUV pulses. By measuring the width of the 2s2p autoionization line of helium, we found the resolution of our spectrometer to be approximately 0.6 eV for electrons at 35.5 eV. Furthermore, the resolution in the 10 to 35 eV range was determined by applying a retarding potential at the entrance of the drift tube.

Monitoring and controlling the electron dynamics in helium with isolated attosecond pulses.

Helium atoms in the presence of extreme ultraviolet light pulses can lose electrons through direct photoionization or through two-electron excitation followed by autoionization. Here we demonstrate that, by combining attosecond extreme ultraviolet pulses with near infrared femtosecond lasers, electron dynamics in helium autoionization can be not only monitored but also controlled. Furthermore, the interference between the two ionization channels was modified by the intense near infrared laser pulse. To the best of our knowledge, this is the first time that double excitation and autoionization were studied experimentally by using isolated attosecond pulses.

Extreme ultraviolet supercontinua supporting pulse durations of less than one atomic unit of time.

Double optical gating of high-harmonic generation was used to obtain supercontinuous spectra in the extreme UV (XUV) region including the water window. The spectra supported a 16 as pulse duration that is below one atomic unit of time (24 as). The dependence of the gated spectra on the carrier-envelope phase of the laser provided evidence that isolated attosecond pulses were generated. In addition, to ensure the temporal coherence of the XUV light, the pulse shape and phase of isolated 107 as XUV pulses using a portion of the spectrum were characterized by attosecond streaking.

Generation of isolated attosecond pulses with 20 to 28 femtosecond lasers.

Isolated attosecond pulses are powerful tools for exploring electron dynamics in matter. So far, such extreme ultraviolet pulses have only been generated using high power, few-cycle lasers, which are very difficult to construct and operate. We propose and demonstrate a technique called generalized double optical gating for generating isolated attosecond pulses with 20 fs lasers from a hollow-core fiber and 28 fs lasers directly from an amplifier. These pulses, generated from argon gas, are measured to be 260 and 148 as by reconstructing the streaked photoelectron spectrograms. This scheme, with a relaxed requirement on laser pulse duration, makes attophysics more accessible to many laboratories that are capable of producing such multicycle laser pulses.

Direct measurement of an electric field in femtosecond Bessel-Gaussian beams.

We demonstrated the mapping of the spatial oscillation of electric fields in the transverse plane of a femtosecond Bessel-Gaussian laser beam from the first principle of classical electrodynamics. An attosecond burst of electrons for probing the electric force was placed in the Bessel beam through photoemission with single isolated 276 as extreme ultraviolet pulses. The direction reversal of the electric field in adjacent Bessel rings was directly confirmed by observing the momentum shift of the probe electrons.