Photosynthesis makes use of sunlight to convert carbon dioxide into useful biomass and is vital for life on Earth. Crucial components for the photosynthetic process are antenna proteins, which absorb light and transmit the resultant excitation energy between molecules to a reaction centre. The efficiency of these electronic energy transfers has inspired much work on antenna proteins isolated from photosynthetic organisms to uncover the basic mechanisms at play. Intriguingly, recent work has documented that light-absorbing molecules in some photosynthetic proteins capture and transfer energy according to quantum-mechanical probability laws instead of classical laws at temperatures up to 180 K. This contrasts with the long-held view that long-range quantum coherence between molecules cannot be sustained in complex biological systems, even at low temperatures. Here we present two-dimensional photon echo spectroscopy measurements on two evolutionarily related light-harvesting proteins isolated from marine cryptophyte algae, which reveal exceptionally long-lasting excitation oscillations with distinct correlations and anti-correlations even at ambient temperature. These observations provide compelling evidence for quantum-coherent sharing of electronic excitation across the 5-nm-wide proteins under biologically relevant conditions, suggesting that distant molecules within the photosynthetic proteins are 'wired' together by quantum coherence for more efficient light-harvesting in cryptophyte marine algae.

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The dynamics of two-dimensional small-polaron formation at ultrathin alkane layers on a silver(111) surface have been studied with femtosecond time- and angle-resolved two-photon photoemission spectroscopy. Optical excitation creates interfacial electrons in quasi-free states for motion parallel to the interface. These initially delocalized electrons self-trap as small polarons in a localized state within a few hundred femtoseconds. The localized electrons then decay back to the metal within picoseconds by tunneling through the adlayer potential barrier. The energy dependence of the self-trapping rate has been measured and modeled with a theory analogous to electron transfer theory. This analysis determines the inter- and intramolecular vibrational modes of the overlayer responsible for self-trapping as well as the relaxation energy of the overlayer molecular lattice. These results for a model interface contribute to the fundamental picture of electron behavior in weakly bonded solids and can lead to better understanding of carrier dynamics in many different systems, including organic light-emitting diodes.

Two-photon photoemission is a promising new technique that has been developed for the study of electron dynamics at interfaces. A femtosecond laser is used to both create an excited electronic distribution at the surface and eject the distribution for subsequent energy analysis. Time- and momentum-resolved two-photon photoemission spectra as a function of layer thickness fully determine the conduction band dynamics at the interface. Earlier clean surface studies showed how excited electron lifetimes are affected by the crystal band structure and vacuum image potential. Recent studies of various insulator/metal interfaces show that the dynamics of excess electrons are largely determined by the electron affinity of the adsorbate. In general, electron dynamics at the interface are influenced by the substrate and adlayer band structures, dielectric screening, and polaron formation in the two-dimensional overlayer lattice.

order provide an opportunity to understand many fundamental physical properties relevant to solar energy conversion. Additionally, organic crystals are promising in their own right due to the effi cient carrier and energy transport properties associated with their long-range order.In particular, crystalline and polycrystalline fi lms of pentacene (PEN) and its derivatives have high carrier mobility for charge transport (≈1−10 cm 2 /Vs hole mobility) [ 1 ] and signifi cant photoconductivity. [ 2,3 ] Moreover, PEN and many of its derivatives display a propensity for singlet fi ssion (SF), [ 4,5 ] a phenomenon that results in greater than 100% internal quantum effi ciency in organic photovoltaics. Numerous possible molecular functionalizations may modify solid-state structural and optoelectronic properties. [ 6 ] Therefore, elucidating the structure-property relation is important for the design of new functional molecular materials. 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-PEN), [ 7 ] shown in Figure 1 , has recently attracted much interest. The bulky groups functionalizing PEN enable solubility in organic solvents and allow for solution-processing of polycrystalline TIPS-PEN thin fi lms with high carrier mobility and photoconductivity. [ 2,3,7 ] While TIPS-PEN apparently retains optical properties similar to PEN, its enhanced carrier mobility [ 8 ] and Relating the Physical Structure and Optoelectronic Function of Crystalline TIPS-PentaceneSahar Sharifzadeh , * Cathy Y. Wong , Hao Wu , Benjamin L. Cotts , Leeor Kronik , Naomi S. Ginsberg , and Jeffrey B. Neaton * Theory and experiment are combined to investigate the nature of low-energy excitons within ordered domains of 6,13-bis(triisopropylsilylethynyl)-pentacene (TIPS-PEN) polycrystalline thin fi lms. First-principles density functional theory and many-body perturbation theory calculations, along with polarizationdependent optical absorption spectro-microscopy on ordered domains, show multiple low-energy absorption peaks that are composed of excitonic states delocalized over several molecules. While the fi rst absorption peak is composed of a single excitonic transition and retains the polarization-dependent behavior of the molecule, higher energy peaks are composed of multiple transitions with optical properties that can not be described by those of the molecule. The predicted structure-dependence of polarization-dependent absorption reveals the exact inter-grain orientation within the TIPS-PEN fi lm. Additionally, the degree of exciton delocalization can be signifi cantly tuned by modest changes in the solid-state structure and the spatial extent of the excitations along a given direction is correlated with the degree of electronic dispersion along the same direction. These fi ndings pave the way for tailoring the singlet fi ssion effi ciency of organic crystals by solid-state structure.

Abstract. We report continuous surface observations of carbon dioxide (CO 2 ) and methane (CH 4 ) from the Los Angeles (LA) Megacity Carbon Project during 2015. We devised a calibration strategy, methods for selection of background air masses, calculation of urban enhancements, and a detailed algorithm for estimating uncertainties in urbanscale CO 2 and CH 4 measurements. These methods are essential for understanding carbon fluxes from the LA megacity and other complex urban environments globally. We estimate background mole fractions entering LA using observations from four "extra-urban" sites including two "marine" sites located south of LA in La Jolla (LJO) and offshore on San Clemente Island (SCI), one "continental" site located in Victorville (VIC), in the high desert northeast of LA, and one "continental/mid-troposphere" site located on Mount Wilson (MWO) in the San Gabriel Mountains. We find that a local marine background can be established to within ∼ 1 ppm CO 2 and ∼ 10 ppb CH 4 using these local measurement sites. Overall, atmospheric carbon dioxide and methane levels are highly variable across Los Angeles. "Urban" and "suburban" sites show moderate to large CO 2 and CH 4 enhancements relative to a marine background estimate. The USC (University of Southern California) site near downtown LA exhibits median hourly enhancements of ∼ 20 ppm CO 2 and ∼ 150 ppb CH 4 during 2015 as well as ∼ 15 ppm CO 2 and ∼ 80 ppb CH 4 during mid-afternoon hours (12:00-16:00 LT, local time), which is the typical period of focus for flux inversions. The estimated measurement uncertainty is typically better than 0.1 ppm CO 2 and 1 ppb CH 4 based on the repeated standard gas measurements from the LA sites during the last 2 years, similar to Andrews et al. (2014). The largest component of the measurement uncertainty is duePublished by Copernicus Publications on behalf of the European Geosciences Union. 8314 K. R. Verhulst et al.: CO 2 and CH 4 measurements from the LA Megacity Carbon Project to the single-point calibration method; however, the uncertainty in the background mole fraction is much larger than the measurement uncertainty. The background uncertainty for the marine background estimate is ∼ 10 and ∼ 15 % of the median mid-afternoon enhancement near downtown LA for CO 2 and CH 4 , respectively. Overall, analytical and background uncertainties are small relative to the local CO 2 and CH 4 enhancements; however, our results suggest that reducing the uncertainty to less than 5 % of the median midafternoon enhancement will require detailed assessment of the impact of meteorology on background conditions.

On the basis of quantum dot exciton states and selection rules for their excitation, a microscopic picture of a nonlinear optical spectroscopy that provides a direct probe of spin relaxation among quantum dot exciton states is described. Equations of motion which govern the evolution of the third order exciton population density are solved numerically to simulate the measured signals. It is shown how cross linearly-polarized pulse sequences in three-pulse transient grating experiments form a polarization grating that monitors the history of the bright exciton ͑F = ±1͒ spin states. Spin flips among those states lead to a decay of the grating, and consequently the diffracted probe signal. In the microscopic picture elucidated from the simulations, destructive interference between the third-order polarizations radiated by populations of excitons with flipped and conserved spin states causes the signal decay. The experiment permits the direct observation of the kinetics of exciton spin state flips in an isotropic ensemble of quantum dots. Such measurements are demonstrated for colloidal CdSe quantum dots at room temperature, and compared with results for a control experiment. The relationship between this experiment and a difference measurement based on circularly-polarized pump and probe pulses is established.

We present an apparatus that noninvasively tracks a moving nanoparticle in three dimensions while providing concurrent sequential spectroscopic measurements. The design, based on confocal microscopy, uses a near-infrared laser and a dark-field condenser for illumination of a gold nanoparticle. By monitoring the scattered light from the nanoparticle and using a piezoelectric stage, the system was able to continuously bring the diffusive particle in a glycerol/water solution back to the focal volume with spatial resolution and response time of less than 210 nm and a millisecond, respectively.