Cluster-Based Approach Utilizing Optimally Tuned TD-DFT to Calculate Absorption Spectra of Organic Semiconductor Thin Films.

The photophysics of organic semiconductor (OSC) thin films or crystals has garnered significant attention in recent years since a comprehensive theoretical understanding of the various processes occurring upon photoexcitation is crucial for assessing the efficiency of OSC materials. To date, research in this area has relied on methods using Frenkel-Holstein Hamiltonians, calculations of the GW-Bethe-Salpeter equation with periodic boundaries, or cluster-based approaches using quantum chemical methods, with each of the three approaches having distinct advantages and disadvantages. In this work, we introduce an optimally tuned, range-separated time-dependent density functional theory approach to accurately reproduce the total and polarization-resolved absorption spectra of pentacene, tetracene, and perylene thin films, all representative OSC materials. Our approach achieves excellent agreement with experimental data (mostly ≤0.1 eV) when combined with the utilization of clusters comprising multiple monomers and a standard polarizable continuum model to simulate the thin-film environment. Our protocol therefore addresses a major drawback of cluster-based approaches and makes them attractive tools for OSC investigations. Its key advantages include its independence from external, system-specific fitting parameters and its straightforward application with well-known quantum chemical program codes. It demonstrates how chemical intuition can help to reduce computational cost and still arrive at chemically meaningful and almost quantitative results.

Surface doping of rubrene single crystals by molecular electron donors and acceptors.

The surface molecular doping of organic semiconductors can play an important role in the development of organic electronic or optoelectronic devices. Single-crystal rubrene remains a leading molecular candidate for applications in electronics due to its high hole mobility. In parallel, intensive research into the fabrication of flexible organic electronics requires the careful design of functional interfaces to enable optimal device characteristics. To this end, the present work seeks to understand the effect of surface molecular doping on the electronic band structure of rubrene single crystals. Our angle-resolved photoemission measurements reveal that the Fermi level moves in the band gap of rubrene depending on the direction of surface electron-transfer reactions with the molecular dopants, yet the valence band dispersion remains essentially unperturbed. This indicates that surface electron-transfer doping of a molecular single crystal can effectively modify the near-surface charge density, while retaining good charge-carrier mobility.

Orbital-resolved observation of singlet fission.

Singlet fission1-13 may boost photovoltaic efficiency14-16 by transforming a singlet exciton into two triplet excitons and thereby doubling the number of excited charge carriers. The primary step of singlet fission is the ultrafast creation of the correlated triplet pair17. Whereas several mechanisms have been proposed to explain this step, none has emerged as a consensus. The challenge lies in tracking the transient excitonic states. Here we use time- and angle-resolved photoemission spectroscopy to observe the primary step of singlet fission in crystalline pentacene. Our results indicate a charge-transfer mediated mechanism with a hybridization of Frenkel and charge-transfer states in the lowest bright singlet exciton. We gained intimate knowledge about the localization and the orbital character of the exciton wave functions recorded in momentum maps. This allowed us to directly compare the localization of singlet and bitriplet excitons and decompose energetically overlapping states on the basis of their orbital character. Orbital- and localization-resolved many-body dynamics promise deep insights into the mechanics governing molecular systems18-20 and topological materials21-23.

Spectroscopic analysis of vibrational coupling in multi-molecular excited states.

Multi-molecular excited states accompanied by intra- and inter-molecular geometric relaxation are commonly encountered in optical and electrooptical studies and applications of organic semiconductors as, for example, excimers or charge transfer states. Understanding the dynamics of these states is crucial to improve organic devices such as light emitting diodes and solar cells. Their full microscopic description, however, demands sophisticated tools such as ab initio quantum chemical calculations which come at the expense of high computational costs and are prone to errors by assumptions as well as iterative algorithmic procedures. Hence, the analysis of spectroscopic data is often conducted at a phenomenological level only. Here, we present a toolkit to analyze temperature dependent luminescence data and gain first insights into the relevant microscopic parameters of the molecular system at hand. By means of a Franck-Condon based approach considering a single effective inter-molecular vibrational mode and different potentials for the ground and excited state we are able to explain the luminescence spectra of such multi-molecular states. We demonstrate that by applying certain reasonable simplifications the luminescence of charge transfer states as well as excimers can be satisfactorily reproduced for temperatures ranging from cryogenics to above room temperature. We present a semi-classical and a quantum-mechanical description of our model and, for both cases, demonstrate its applicability by analyzing the temperature dependent luminescence of the amorphous donor-acceptor heterojunction tetraphenyldibenzoperiflanthene:C60 as well as polycrystalline zinc-phthalocyanine to reproduce the luminescence spectra and extract relevant system parameters such as the excimer binding energy.

Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2'-yl)-o-carborane.

Reversible conversion between excited-states plays an important role in many photophysical phenomena. Using 1-(pyren-2'-yl)-o-carborane as a model, we studied the photoinduced reversible charge-transfer (CT) process and the thermodynamic equilibrium between the locally-excited (LE) state and CT state, by combining steady state, time-resolved, and temperature-dependent fluorescence spectroscopy, fs- and ns-transient absorption, and DFT and LR-TDDFT calculations. Our results show that the energy gaps and energy barriers between the LE, CT, and a non-emissive 'mixed' state of 1-(pyren-2'-yl)-o-carborane are very small, and all three excited states are accessible at room temperature. The internal-conversion and reverse internal-conversion between LE and CT states are significantly faster than the radiative decay, and the two states have the same lifetimes and are in thermodynamic equilibrium.

Accurate Polarization-Resolved Absorption Spectra of Organic Semiconductor Thin Films Using First-Principles Quantum-Chemical Methods: Pentacene as a Case Study.

Theoretical studies using clusters as model systems have been extremely successful in explaining various photophysical phenomena in organic semiconductor (OSC) thin films. But they have not been able to satisfactorily simulate total and polarization-resolved absorption spectra of OSCs so far. In this work, we demonstrate that accurate spectra are predicted by time-dependent density functional theory (TD-DFT) when the employed cluster reflects the symmetry of the crystal structure and all monomers feel the same environment. Additionally, long-range corrected optimal tuned functionals are mandatory. For pentacene thin films, the computed electronic spectra for thin films then reach an impressive accuracy compared with experimental data with a deviation of less than 0.1 eV. This allows for accurate peak assignments and mechanistic studies, which paves the way for a comprehensive understanding of OSCs using an affordable and easy-to-use cluster approach.

Quantitative monitoring of paramagnetic contrast agents and their allocation in plant tissues via DCE-MRI.

BACKGROUND: Studying dynamic processes in living organisms with MRI is one of the most promising research areas. The use of paramagnetic compounds as contrast agents (CA), has proven key to such studies, but so far, the lack of appropriate techniques limits the application of CA-technologies in experimental plant biology. The presented proof-of-principle aims to support method and knowledge transfer from medical research to plant science. RESULTS: In this study, we designed and tested a new approach for plant Dynamic Contrast Enhanced Magnetic Resonance Imaging (pDCE-MRI). The new approach has been applied in situ to a cereal crop (Hordeum vulgare). The pDCE-MRI allows non-invasive investigation of CA allocation within plant tissues. In our experiments, gadolinium-DTPA, the most commonly used contrast agent in medical MRI, was employed. By acquiring dynamic T1-maps, a new approach visualizes an alteration of a tissue-specific MRI parameter T1 (longitudinal relaxation time) in response to the CA. Both, the measurement of local CA concentration and the monitoring of translocation in low velocity ranges (cm/h) was possible using this CA-enhanced method. CONCLUSIONS: A novel pDCE-MRI method is presented for non-invasive investigation of paramagnetic CA allocation in living plants. The temporal resolution of the T1-mapping has been significantly improved to enable the dynamic in vivo analysis of transport processes at low-velocity ranges, which are common in plants. The newly developed procedure allows to identify vascular regions and to estimate their involvement in CA allocation. Therefore, the presented technique opens a perspective for further development of CA-aided MRI experiments in plant biology.

Color-Switchable Subwavelength Organic Light-Emitting Antennas.

Future photonic devices require efficient, multifunctional, electrically driven light sources with directional emission properties and subwavelength dimensions. Electrically driven plasmonic nanoantennas have been demonstrated as enabling technology. Here, we present the concept of a nanoscale organic light-emitting antenna (OLEA) as a color- and directionality-switchable point source. The device consists of laterally arranged electrically contacted gold nanoantennas with their gap filled by the organic semiconductor zinc phthalocyanine (ZnPc). Since ZnPc shows preferred hole conduction in combination with gold, the recombination zone relocates depending on the polarity of the applied voltage and couples selectively to either of the two antennas. Thereby, the emission characteristics of the device also depend on polarity. Contrary to large-area OLEDs where recombination at metal contacts significantly contributes to losses, our ultracompact OLEA structures facilitate efficient radiation into the far-field rendering transparent electrodes obsolete. We envision OLEA structures to serve as wavelength-scale pixels with tunable color and directionality for advanced display applications.

Nuclear dynamics of singlet exciton fission in pentacene single crystals.

Singlet exciton fission (SEF) is a key process for developing efficient optoelectronic devices. An aspect rarely probed directly, yet with tremendous impact on SEF properties, is the nuclear structure and dynamics involved in this process. Here, we directly observe the nuclear dynamics accompanying the SEF process in single crystal pentacene using femtosecond electron diffraction. The data reveal coherent atomic motions at 1 THz, incoherent motions, and an anisotropic lattice distortion representing the polaronic character of the triplet excitons. Combining molecular dynamics simulations, time-dependent density-functional theory, and experimental structure factor analysis, the coherent motions are identified as collective sliding motions of the pentacene molecules along their long axis. Such motions modify the excitonic coupling between adjacent molecules. Our findings reveal that long-range motions play a decisive part in the electronic decoupling of the electronically correlated triplet pairs and shed light on why SEF occurs on ultrafast time scales.

Spatial Anisotropy of Charge Transfer at Perfluoropentacene-Pentacene (001) Single-Crystal Interfaces and its Relevance for Thin Film Devices.

Archetypal donor-acceptor (D-A) interfaces composed of perfluoropentacene (PFP) and pentacene (PEN) are examined for charge transfer (CT) state formation and energetics as a function of their respective molecular configuration. To exclude morphological interference, our structural as well as highly sensitive differential reflectance spectroscopy studies were carried out on PFP thin films epitaxially grown on PEN(001) single-crystal facets. Whereas the experimental data supported by complementary theoretical calculations confirm the formation of a strong CT state in the case of a cofacial PFP-PEN stacking, CT formation is energetically less favorable and thus absent for the corresponding head-to-tail configuration as disclosed for the first time. In view of technological implementations, the knowledge gained on the single-crystal references is transferred to thin-film diodes composed of either stacked PFP/PEN bilayers or mixed PFP:PEN heterojunction interfaces. As demonstrated, their electronic and electroluminescent behavior can be consistently described by the absence or presence of interfacial CT states. Thus, our results hint at the thorough design of D-A interfaces to achieve the highest device performances.

Adaptation to Host-Specific Bacterial Pathogens Drives Rapid Evolution of a Human Innate Immune Receptor.

The selective pressure by infectious agents is a major driving force in the evolution of humans and other mammals. Members of the carcinoembryonic antigen-related cell adhesion molecule (CEACAM) family serve as receptors for bacterial pathogens of the genera Haemophilus, Helicobacter, Neisseria, and Moraxella, which engage CEACAMs via distinct surface adhesins. While microbial attachment to epithelial CEACAMs facilitates host colonization, recognition by CEACAM3, a phagocytic receptor expressed by granulocytes, eliminates CEACAM-binding bacteria. Sequence analysis of primate CEACAM3 orthologs reveals that this innate immune receptor is one of the most rapidly evolving human proteins. In particular, the pathogen-binding extracellular domain of CEACAM3 shows a high degree of non-synonymous versus synonymous nucleotide exchanges, indicating an exceptionally strong positive selection. Using CEACAM3 domains derived from different primates, we find that the amino acid alterations found in CEACAM3 translate into characteristic binding patterns for bacterial adhesins. One such amino acid residue is F62 in human and chimp CEACAM3, which is not present in other primates and which is critical for binding the OMP P1 adhesin of Haemophilus aegyptius. Incorporation of the F62-containing motif into gorilla CEACAM3 results in a gain-of-function phenotype with regard to phagocytosis of H. aegyptius. Moreover, CEACAM3 polymorphisms found in human subpopulations widen the spectrum of recognized bacterial adhesins, suggesting an ongoing multivariate selection acting on this innate immune receptor. The species-specific detection of diverse bacterial adhesins helps to explain the exceptionally fast evolution of CEACAM3 within the primate lineage and provides an example of Red Queen dynamics in the human genome.

Scalable and Transfer-Free Fabrication of MoS2/SiO2 Hybrid Nanophotonic Cavity Arrays with Quality Factors Exceeding 4000.

We report the fully-scalable fabrication of a large array of hybrid molybdenum disulfide (MoS2) - silicon dioxide (SiO2) one-dimensional, free-standing photonic-crystal cavities capable of enhancement of the MoS2 photoluminescence at the narrow cavity resonance. We demonstrate continuous tunability of the cavity resonance wavelength across the entire emission band of MoS2 simply by variation of the photonic crystal periodicity. Device fabrication started by substrate-scale growth of MoS2 using chemical vapor deposition (CVD) on non-birefringent thermal oxide on a silicon wafer; it was followed by lithographic fabrication of a photonic crystal nanocavity array on the same substrate at more than 50% yield of functional devices. Our cavities exhibit three dominant modes with measured linewidths less than 0.2 nm, corresponding to quality factors exceeding 4000. All experimental findings are found to be in excellent agreement with finite difference time domain (FDTD) simulations. CVD MoS2 provides scalable access to a direct band gap, inorganic, stable and efficient emitter material for on-chip photonics without the need for epitaxy and is at CMOS compatible processing parameters even for back-end-of-line integration; our findings suggest feasibility of cavity based line-narrowing in MoS2-based on-chip devices as it is required for instance for frequency-multiplexed operation in on-chip optical communication and sensing.

2,4-Diaminopyrimidines as dual ligands at the histamine H1 and H4 receptor-H1/H4-receptor selectivity.

Distinct diaminopyrimidines, for example, 4-(4-methylpiperazin-1-yl)-5,6-dihydrobenzo[h]quinazolin-2-amine are histamine H4 receptor (H4R) antagonists and show high affinity to the H4R, but only a moderate affinity to the histamine H1 receptor (H1R). Within previous studies it was shown that an aromatic side chain with a distinct distance to the basic amine and aromatic core is necessary for affinity to the human H1R (hH1R). Thus, a rigid aminopyrimidine with a tricyclic core was used as a lead structure. There, (1) the flexible aromatic side chain was introduced, (2) the substitution pattern of the pyrimidine core was exchanged and (3) rigidity was decreased by opening the tricyclic core. Within the present study, two compounds with similar affinity in the one digit µM range to the human H1R and H4R were identified. While the affinity at the hH1R increased about 4- to 8-fold compared to the parent diaminopyrimidine, the affinity to the hH4R decreased about 5- to 8-fold. In addition to the parent diaminopyrimidine, two selected compounds were docked into the H1R and H4R and molecular dynamic studies were performed to predict the binding mode and explain the experimental results on a molecular level. The two new compounds may be good lead structures for the development of dual H1/H4 receptor ligands with affinities in the same range.

Long-term beneficial effect of a 16-week very low calorie diet on pericardial fat in obese type 2 diabetes mellitus patients.

Pericardial fat accumulation has been associated with an increased cardiovascular risk. A very low calorie diet (VLCD) improves the cardiovascular risk profile in patients with type 2 diabetes mellitus (T2DM), by improving the metabolic profile, heart function, and triglyceride (TG) stores in (non)adipose tissues. However, long-term effects of a VLCD on pericardial fat volume and tissue-specific TG accumulation have not been documented. The aim of this study was therefore to assess the effects of a 16-week VLCD and of subsequent 14 months follow-up on a regular diet on pericardial fat in relation to other TG stores in obese T2DM patients. We included 14 obese patients with insulin-treated T2DM (mean ± s.e.m.: age 53 ± 2 years; BMI 35 ± 1 kg/m(2)). Pericardial fat and other (non)adipose TG stores were measured using magnetic resonance (MR) imaging and proton spectroscopy before and after a 16-week VLCD and after a 14-month follow-up without dietary interventions. A 16-week VLCD reduced body weight, pericardial fat, hepatic TG content, visceral and subcutaneous abdominal fat volumes to 78, 83, 16, 40, and 53% of baseline values respectively, (all P < 0.05). After an additional 14 months of follow-up on a regular diet, the reduction in pericardial fat volume sustained, despite a substantial regain in body weight, visceral abdominal fat, and hepatic TG content (respectively 90, 83 and 73% of baseline values). In conclusion, VLCD-induced weight loss in obese T2DM patients is accompanied by a substantial decrease in pericardial fat volume, which is sustained even after subsequent weight regain.