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OMIECs undergo structural rearrangements to accommodate ions and electronic charge carriers during which percolating networks are formed for efficient electronic charge transport.

Ocean mesoscale and submesoscale features, such as eddies and filaments, play a key role in the foraging ecology of marine predators, by concentrating nutrients and acting as aggregative structures for pelagic organisms. Highly pelagic seabirds may exploit these features to find profitable food patches in a dynamic and complex 3-dimensional spatial environment. Using miniaturized GPS loggers, we investigated whether foraging habitat selection of the Mediterranean storm petrel Hydrobates pelagicus melitensis, one of the smallest (ca. 28 g) seabirds worldwide, was affected by different static and dynamic oceanographic features during the breeding period. Individuals performed long foraging trips (up to 1113 km) in a relatively short time (1 to 2 d), covering large home ranges (up to 34370 km2), particularly during incubation. Different oceanographic features affected the at-sea distribution of storm petrels at different spatio-temporal scales. During incubation, individuals selected areas characterized by shallow waters and strong currents, conditions that may enhance vertical water mixing and increase food availability. During chick-rearing, they foraged closer to the colony, selecting shallow and productive areas, where increasing Lagrangian coherent structures and eddy kinetic energy enhanced foraging probability. These features could play an important role in storm petrels’ foraging habitat selection, especially during chick-rearing, given their need to find predictable food patches in a short timespan. Overall, our results suggest that marine circulation processes are key drivers of the at-sea distribution of this small pelagic surface predator.

Understanding sediment transport dynamics is key to understanding landscape evolution, and has important implications for engineering projects, aquatic ecosystem dynamics, and transmission of water-borne diseases. Multiple elevated temperature infra-red stimulated luminescence (MET-IRSL) has great potential to provide detailed information on the transport of sediments using infra-red light to stimulate the luminescence signal of feldspars. MET-IRSL uses a series of elevated temperature stimulations to access multiple signals with different characteristic rates of signal reduction by light exposure (bleaching), for example, during grain transport. During deposition and storage, trapped charge accumulates, leading to growth of the different IRSL signals, until the grain is again subject to transport. Applied in this manner, MET-IRSL measurements can constrain past sediment burial and exposure histories.MET-IRSL measurements of different grain and clast sizes (e.g. silt, sand, pebbles and cobbles) can provide a range of sediment transport information, providing further constraint to sediment dynamics and system behaviour. Different clast size groups are associated with varied ways to structure the MET-IRSL measurements, e.g. depth bleaching profiles observed within pebbles and cobbles. In this presentation we demonstrate the potential of combining these approaches, and of constructing time-space equivalence models for real world situations, including the site of Allt Dubhaig, Perthshire, Scotland.

The efficiency of bulk heterojunction (BHJ) organic photovoltaic (OPV) devices depends significantly upon absorption of photons and the migration of the photogenerated excited state to the heteroju...

Unlike the Frenkel exciton model, the essential state model (ESM) for aggregates of donor–acceptor (DA) chromophores accounts self-consistently for the effect of the reaction field on the ground an...

The exciton band dispersion in π-stacks of conjugated organic chromophores is a critical factor in determining the photophysical response and transport properties. In such stacks, the exciton band ...

The essential states model (ESM) for donor–acceptor–donor (D–A–D) chromophores is used to explore absorption and photoluminescence (PL) in molecular dimers composed of centrosymmetric and non-centrosymmetric squaraine molecules. The spectral line shapes and shifts relative to the monomer spectrum are due to an interesting interplay between three-center charge distributions responsible for ground- and excited-state (permanent) dipole and quadrupole moments and two-center charge distributions responsible for transition dipole moments. The Davydov splitting is sensitive only to the interactions between the (extended) transition dipoles , whereas the permanent dipole-dipole and quadruple-quadrupole interactions impact the midpoint frequency of the two Davydov components, leading to a generally asymmetric splitting relative to the peak monomer transition frequency. The theory accurately reproduces the steady-state absorption and PL line shapes recently obtained for covalently bound squaraine dimers. The ESM also predicts an extreme type of non-Kasha behavior, where both Davydov components are blue-shifted above the monomer transition frequency.

An extension of the essential states model is developed to investigate the absorption and electronic properties of a highly dipolar merocyanine dye and double and quadruple π-stacks formed upon the...

The shape of the mid-IR absorption spectrum provides valuable information about the “hole” polaron coherence length in doped and undoped conjugated polymer films. In poly(3-hexylthiophene) (P3HT) f...

A highly sensitive short-wave infrared (SWIR, λ > 1000 nm) organic photodiode (OPD) is described based on a well-organized nanocrystalline bulk-heterojunction (BHJ) active layer composed of a dicyanovinyl-functionalized squaraine dye (SQ-H) donor material in combination with PC\(_{61}\)BM. Through thermal annealing, dipolar SQ-H chromophores self-assemble in a nanoscale structure with intermolecular charge transfer mediated coupling, resulting in a redshifted and narrow absorption band at 1040 nm as well as enhanced charge carrier mobility. The optimized OPD exhibits an external quantum efficiency (EQE) of 12.3% and a full-width at half-maximum of only 85 nm (815 cm\(^{-1}\)) at 1050 nm under 0 V, which is the first efficient SWIR OPD based on J-type aggregates. Photoplethysmography application for heart-rate monitoring is successfully demonstrated on flexible substrates without applying reverse bias, indicating the potential of OPDs based on short-range coupled dye aggregates for low-power operating wearable applications.

The Mediterranean islands’ blue economy and, more specifically, the tourism sector, largely regulate Europe’s gross product. Climate change threatens the ecological, societal, and economic sustainability of the islands in many ways, with increasing wildfires making up one of the most critical components of the climate change impacts on tourism. Here, we aim to identify and assess forest fire vulnerability and risk due to climate change for seven Mediterranean islands through the application of the “impact chain” conceptual framework. The backbone of this approach requires the integration of quantitative and qualitative data according to the three main risk components sensu the Intergovernmental Panel on Climate Change (IPCC), i.e., hazard, exposure, and vulnerability, with a structured participatory approach involving stakeholders and experts. Our results illustrate the islands with high potential for improvement in terms of adapting capacity and, by indicating the contribution of the different risk components, highlight the main environmental and socio-economic elements that affect the islands’ vulnerability and risk under climate change. The approach’s potentials and constraints are discussed, suggesting that the method can be handily used to point out the priorities that must be addressed by mitigation and adaptation policies and measures at the island level. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

ConspectusExcitons and polarons play a central role in the electronic and optical properties of organic semiconducting polymers and molecular aggregates and are of fundamental importance in understanding the operation of organic optoelectronic devices such as solar cells and light-emitting diodes. For many conjugated organic molecules and polymers, the creation of neutral electronic excitations or ionic radicals is associated with significant nuclear relaxation, the bulk of which occurs along the vinyl-stretching mode or the aromatic-quinoidal stretching mode when conjugated rings are present. Within a polymer chain or molecular aggregate, nuclear relaxation competes with energy- and charge-transfer, mediated by electronic interactions between the constituent units (repeat units for polymers and individual chromophores for a molecular aggregate); for neutral electronic excitations, such inter-unit interactions lead to extended excited states or excitons, while for positive (or negative) charges, interactions lead to delocalized hole (or electron) polarons. The electronic coupling as well as the local coupling between electronic and nuclear degrees of freedom in both excitons and polarons can be described with a Holstein Hamiltonian. However, although excitons and polarons derive from similarly structured Hamiltonians, their optical signatures are quite distinct, largely due to differing ground states and optical selection rules.In this Account, we explore the similarities and differences in the spectral response of excitons and polarons in organic polymers and molecular aggregates. We limit our analysis to the subspace of excitons and hole polarons containing at most one excitation; hence we omit the influence of bipolarons, biexcitons, and higher multiparticle excitations. Using a generic linear array of coupled units as a model host for both excitons and polarons, we compare and contrast the optical responses of both quasiparticles, with a particular emphasis on the spatial coherence length, the length over which an exciton or polaron possesses wave-like properties important for more efficient transport. For excitons, the UV-vis absorption spectrum is generally represented by a distorted vibronic progression with H-like or J-like signatures depending on the sign of the electronic coupling, Jex. The spectrum broadens with increasing site disorder, with the spectral area preserved due to an oscillator strength sum rule. For (hole) polarons, the generally stronger electronic coupling results in a mid-IR spectrum consisting of a narrow, low-energy peak (A) with energy near a vibrational quantum of the vinyl stretching mode, and a broader, higher-energy feature (B). In contrast to the UV-vis spectrum, the mid-IR spectrum is invariant to the sign of the electronic coupling, th, and completely resistant to long-range disorder, where it remains entirely homogeneously broadened. Even in the presence of short-range disorder, the width of peak A remains surprisingly narrow as long as |th| remains sufficiently large, a property that can be understood in terms of Herzberg-Teller coupling. Unlike for excitons, for polarons, the absorption spectral area decreases with increasing short-range disorder σ (i.e., there is no oscillator sum rule) reflective of a decreasing polaron coherence length. The intensity of the low-energy peak A in relation to B is an important signature of polaron coherence. By contrast, for excitons, the absorption spectrum contains no unambiguous signs of exciton coherence. One must instead resort to the shape of the steady-state photoluminescence spectrum. The Holstein-based model has been highly successful in accounting for the spectral properties of molecular aggregates as well as conjugated polymers like poly(3-hexylthiophene) (P3HT) in the mid-IR and UV-vis spectral regions.

Advances in protein design and engineering have yielded peptide assemblies with enhanced and non-native functionalities. Here, various molecular organic semiconductors (OSCs), with known excitonic up- and down-conversion properties, are attached to a de novo-designed protein, conferring entirely novel functions on the peptide scaffolds. The protein-OSC complexes form similarly sized, stable, water-soluble nanoparticles that are robust to cryogenic freezing and processing into the solid-state. The peptide matrix enables the formation of protein-OSC-trehalose glasses that fix the proteins in their folded states under oxygen-limited conditions. The encapsulation dramatically enhances the stability of protein-OSC complexes to photodamage, increasing the lifetime of the chromophores from several hours to more than 10 weeks under constant illumination. Comparison of the photophysical properties of astaxanthin aggregates in mixed-solvent systems and proteins shows that the peptide environment does not alter the underlying electronic processes of the incorporated materials, exemplified here by singlet exciton fission followed by separation into weakly bound, localized triplets. This adaptable protein-based approach lays the foundation for spectroscopic assessment of a broad range of molecular OSCs in aqueous solutions and the solid-state, circumventing the laborious procedure of identifying the experimental conditions necessary for aggregate generation or film formation. The non-native protein functions also raise the prospect of future biocompatible devices where peptide assemblies could complex with native and non-native systems to generate novel functional materials.

Polaritons in an ensemble of permutationally symmetric chromophores confined to an optical microcavity are investigated numerically. The analysis is based on the Holstein–Tavis–Cummings Hamiltonian which accounts for the coupling between an electronic excitation on each chromophore and a single cavity mode, as well as the coupling between the electronic and nuclear degrees of freedom on each chromophore. A straightforward ensemble partitioning scheme is introduced, which, along with an intuitive ansatz, allows one to obtain accurate evaluations of the lowest-energy polaritons using a subset of collective states. The polaritons include all three degrees of freedom—electronic, vibronic, and photonic—and can therefore be described as exciton–phonon polaritons. Applications focus on the limiting regimes where the Rabi frequency is small or large compared to the nuclear relaxation energy subsequent to optical excitation, with relaxation occurring mainly along the vinyl stretching coordinate in conjugated organic chromophores. Comparisons are also made to the more conventional vibronic polariton approach, which does not take into account two-particle excitations and vibration–photon states.

Aggregates of quadrupolar DAD-type chromophores are investigated theoretically using the essential states model (ESM) enhanced to include vibronic coupling. On the basis of vibronic signatures in the absorption and photoluminescence spectra, important connections are made to the Frenkel exciton model, which is the basis for defining conventional H- and J-aggregates. In contrast to the exciton theory, the ESM allows for an unusual type of the red-shifted H-aggregate, driven by the large quadrupole–quadrupole interaction. Except for the red shift of the main absorption peak, such aggregates display all of the characteristics of conventional H-aggregates, including suppressed radiative decay rates and all of the vibronic signatures in the absorption and photoluminescence spectra consistent with Frenkel exciton models. Red-shifted H-dimers occur for a range of slip angles, which separate conventional H- and J-aggregate behavior, with the slip range diminishing with increasing intermolecular separation. Davydo...

For the prototypical two-dimensional hybrid organic–inorganic perovskites (2D HOIPs) (AE4T)PbX4 (X = Cl, Br, and I), we demonstrate that the Frenkel–Holstein Hamiltonian (FHH) can be applied to describe the absorption spectrum arising from the organic component. We first model the spectra using only the four nearest neighbor couplings between translationally inequivalent molecules in the organic herringbone lattice as fitting parameters in the FHH. We next use linear-response time-dependent density functional theory (LR-TDDFT) to calculate molecular transition densities, from which extended excitonic couplings are evaluated based on the atomic positions within the 2D HOIPs. We find that both approaches reproduce the experimentally observed spectra, including changes in their shape and peak positions. The spectral changes are correlated with a decrease in excitonic coupling from X = Cl to X = I. Importantly, the LR-TDDFT-based approach with extended excitonic couplings not only gives better agreement with the experimental absorption line shape than the approach using a restricted set of fitted parameters but also allows us to relate the changes in excitonic coupling to the underlying geometry. We accordingly find that the decrease in excitonic coupling from X = Cl to Br to I is due to an increase in molecular separation, which in turn can be related to the increasing Pb–X bond length from Cl to I. Our research opens up a potential pathway to predicting optoelectronic properties of new 2D HOIPs from ab initio calculations and to gain insight into structural relations from 2D HOIP absorption spectra.

The origin of the mid-infrared (IR) spectral features for hole absorption in doped poly(3-hexylthiophene) (P3HT) films is investigated theoretically and experimentally. Using a Holstein-style Hamil...

The electronic excited states of molecular aggregates and their photophysical signatures have long fascinated spectroscopists and theoreticians alike since the advent of Frenkel exciton theory almost 90 years ago. The influence of molecular packing on basic optical probes like absorption and photoluminescence was originally worked out by Kasha for aggregates dominated by Coulombic intermolecular interactions, eventually leading to the classification of J- and H-aggregates. This review outlines advances made in understanding the relationship between aggregate structure and photophysics when vibronic coupling and intermolecular charge transfer are incorporated. An assortment of packing geometries is considered from the humble molecular dimer to more exotic structures including linear and bent aggregates, two-dimensional herringbone and "HJ" aggregates, and chiral aggregates. The interplay between long-range Coulomb coupling and short-range charge-transfer-mediated coupling strongly depends on the aggregate architecture leading to a wide array of photophysical behaviors.