Mcintyrehurst7626

As the oscillator strength is increased, we find that a new mode emerges between these upper and lower polariton states and show that this new mode is an excitonic surface mode. Our study also features an exploration of the role played by the orientation of the excitonic dipole moment and the relationship between the modes we observe and the transverse and longitudinal resonances associated with the excitonic response. We also investigate why this type of double splitting is rarely observed in experiments.Within the self-consistent field approximation, computationally tractable expressions for the isotropic second-order hyperpolarizability have been derived and implemented for the calculation of two-photon absorption cross sections. The novel tensor average formulation presented in this work allows for the evaluation of isotropic damped cubic response functions using only ∼3.3% (one-photon off-resonance regions) and ∼10% (one-photon resonance regions) of the number of auxiliary Fock matrices required when explicitly calculating all the needed individual tensor components. Numerical examples of the two-photon absorption cross section in the one-photon off-resonance and resonance regions are provided for alanine-tryptophan and 2,5-dibromo-1,4-bis(2-(4-diphenylaminophenyl)vinyl)-benzene. Furthermore, a benchmark set of 22 additional small- and medium-sized organic molecules is considered. In all these calculations, a quantitative assessment is made of the reduced and approximate forms of the cubic response function in the one-photon off-resonance regions and results demonstrate a relative error of less than ∼5% when using the reduced expression as compared to the full form of the isotropic cubic response function.Cross-linked polyethylene (XLPE) has been recognized as an outstanding insulator for high-voltage power cables due to its favorable structural integrity at high temperature, low moisture sensitivity, chemical resistance, and low rates of failure due to aging. However, the roles of by-products and amorphous regions generated during the XLPE production are not clearly known at the atomistic scale. In this study, we present an eReaxFF-based molecular dynamics simulation framework with an explicit electron description verified against density functional theory data to investigate the roles of XLPE by-products and processing variables such as density and voids on the time to dielectric breakdown (TDDB) of polyethylene (PE). Our simulation results indicate that an increase in density of PE increases the TDDB; however, adding a by-product with positive electron affinity such as acetophenone can reduce the TDDB. Furthermore, during the electrical breakdown in PE, electrons tend to migrate through voids when transferring from the anode to cathode. In comparison with neutral acetophenone, we find that the acetophenone radical anion can significantly reduce the energy barrier and the reaction energy of secondary chemical reactions.The question of classicality is addressed in relation with the shape of the nuclear skeleton of molecular systems. As the most natural environment, the electrons of the molecule are considered as continuously monitoring agents for the nuclei. For this picture, an elementary formalism of decoherence theory is developed and numerical results are presented for few-particle systems. The numerical examples suggest that the electron-nucleus Coulomb interaction is sufficient for inducing a blurred shape with strong quantum coherences in compounds of the lightest elements, H2, D2, T2, and HeH+.The many-body expansion (MBE) of energies of molecular clusters or solids offers a way to detect and analyze errors of theoretical methods that could go unnoticed if only the total energy of the system was considered. In this regard, the interaction between the methane molecule and its enclosing dodecahedral water cage, CH4···(H2O)20, is a stringent test for approximate methods, including density functional theory (DFT) approximations. Hybrid and semilocal DFT approximations behave erratically for this system, with three- and four-body nonadditive terms having neither the correct sign nor magnitude. Here, we analyze to what extent these qualitative errors in different MBE contributions are conveyed to post-Kohn-Sham random-phase approximation (RPA), which uses approximate Kohn-Sham orbitals as its input. The results reveal a correlation between the quality of the DFT input states and the RPA results. Moreover, the renormalized singles energy (RSE) corrections play a crucial role in all orders of the many-body expansion. For dimers, RSE corrects the RPA underbinding for every tested Kohn-Sham model generalized-gradient approximation (GGA), meta-GGA, (meta-)GGA hybrids, as well as the optimized effective potential at the correlated level. Remarkably, the inclusion of singles in RPA can also correct the wrong signs of three- and four-body nonadditive energies as well as mitigate the excessive higher-order contributions to the many-body expansion. The RPA errors are dominated by the contributions of compact clusters. As a workable method for large systems, we propose to replace those compact contributions with CCSD(T) energies and to sum up the remaining many-body contributions up to infinity with supermolecular or periodic RPA. As a demonstration of this approach, we show that for RPA(PBE0)+RSE it suffices to apply CCSD(T) to dimers and 30 compact, hydrogen-bonded trimers to get the methane-water cage interaction energy to within 1.6% of the reference value.Nanoplastics with small particle sizes and high surface area/volume ratios easily absorb environmental pollutants and affect their bioavailability. In this study, polystyrene nanoplastic beads (PS-NPBs) with a particle size of 100 nm and butyl methoxydibenzoylmethane (BMDBM) sunscreen in personal-care products were chosen as target pollutants to study their developmental toxicity and interactive effects on zebrafish embryos. The exposure period was set from 2 to 12 h postfertilization (hpf). Trametinib BMDBM and PS-NPBs significantly upregulated genes related to antioxidant enzymes and downregulated the gene expression of aromatase and DNA methyltransferases, but the influenced genes were not exactly the same. The combined exposure reduced the adverse effects on the expression of all genes. With the help of the single-cell RNA sequencing technology, neural mid cells were identified as the target cells of both pollutants, and brain development, head development, and the notch signaling pathway were the functions they commonly altered. The key genes and functions that are specifically affected by BMDBM and/or PS-NPBs were identified. BMDBM mainly affects the differentiation and fate of neurons in the central nervous system through the regulation of her5, her6, her11, lfng, pax2a, and fgfr4. The PS-NPBs regulate the expression of olig2, foxg1a, fzd8b, six3a, rx1, lhx2b, nkx2.1a, and sfrp5 to alter nervous system development, retinal development, and stem cell differentiation. The phenotypic responses of zebrafish larvae at 120 hpf were tested, and significant inhibition of locomotor activity was found, indicating that early effects on the central nervous system would have a sustained impact on the behavior of zebrafish.Here we report an anionic meso-tetrakis(4-carboxymethylthio-2,3,5,6-tetrafluorophenyl) zinc porphyrin (ZnTF4PPTC4-) to form a supramolecular complex with a cationic lithium endohedral [60]fullerene (Li+@C60). The supramolecular ZnTF4PPTC4-/Li+@C60 complex formed by strong electrostatic attraction with a large binding constant generates a long-lived charge-separated (CS) state with low energy loss by photoinduced electron transfer from ZnTF4PPTC4- to Li+@C60. The anionic fluorinated zinc porphyrin with high oxidation potential reduces the energy loss associated with the charge separation and enhances the energy level of the CS state. The energy level of the CS state determined by electrochemical measurements is at 0.94 eV, which is much higher than that of a similar supramolecular complex using an anionic meso-tetrakis(sulfonatophenyl) zinc porphyrin (ZnTPPS4-) at 0.55 eV. Time-resolved transient absorption spectroscopy demonstrates that ZnTF4PPTC4-/Li+@C60 generates a long-lived CS state with a lifetime of 0.29 ms in a binary solvent of acetonitrile and chlorobenzene. The lifetime of the CS state is comparable to that of ZnTPPS4-/Li+@C60 in benzonitrile.Bioimaging is a powerful strategy for studying biological activities, which is still limited by the difficulty of distinguishing obscured signals from high background. Despite the development of various new imaging materials and methods, target signals are still likely to be submerged in spontaneous fluorescence or scattering signals. Herein, a novel two-photon excitation-process-based imaging postprocessing algorithm model (2PIA) is introduced to minimize background noise, and triplet-triplet annihilation upconversion metal-organic frameworks (UCMOFs) are chosen as demonstration. Through the collection of several image stacks, the related polynomial of the luminescence intensity and excitation power was established, following splitting the desired signals from noise and obtaining the background-free images definitely. Both in vitro and in vivo experiments show that improved signal visibility is achieved through 2PIA and UCMOFs by removing the interference of scattering, bioluminescence, and other fluorescence materials. The imaging spatial resolution and tissue penetration depth were greatly enhanced. Benefiting from 2PIA, as low as 100 UCMOFs labeled cells can be identified from obscuring background easily after intravenous injection. This image postprocessing method combined with special two-photon excited luminescent materials can conduct biological imaging from complex background interference without using expensive instruments or delicate materials, which holds great promise for accurate biological imaging.Infrared-to-visible photon upconversion could benefit applications such as photovoltaics, infrared sensing, and bioimaging. Solid-state upconversion based on triplet exciton annihilation sensitized by nanocrystals is one of the most promising approaches, albeit limited by relatively weak optical absorption. Here, we integrate the upconverting layers into a Fabry-Pérot microcavity with quality factor Q = 75. At the resonant wavelength λ = 980 nm, absorption increases 74-fold and we observe a 227-fold increase in the intensity of upconverted emission. The threshold excitation intensity is reduced by 2 orders of magnitude to a subsolar flux of 13 mW/cm2. We measure an external quantum efficiency of 0.06 ± 0.01% and a 2.2-fold increase in the generation yield of upconverted photons. Our work highlights the potential of triplet-triplet annihilation-based upconversion in low-intensity sensing applications and demonstrates the importance of photonic designs in addition to materials engineering to improve the efficiency of solid-state upconversion.Nanomaterial (NM) delivery to solid tumors has been the focus of intense research for over a decade. Classically, scientists have tried to improve NM delivery by employing passive or active targeting strategies, making use of the so-called enhanced permeability and retention (EPR) effect. This phenomenon is made possible due to the leaky tumor vasculature through which NMs can leave the bloodstream, traverse through the gaps in the endothelial lining of the vessels, and enter the tumor. Recent studies have shown that despite many efforts to employ the EPR effect, this process remains very poor. Furthermore, the role of the EPR effect has been called into question, where it has been suggested that NMs enter the tumor via active mechanisms and not through the endothelial gaps. In this review, we provide a short overview of the EPR and mechanisms to enhance it, after which we focus on alternative delivery strategies that do not solely rely on EPR in itself but can offer interesting pharmacological, physical, and biological solutions for enhanced delivery.