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Lcd exosomal proteomic reports of corneal epithelial damage in person suffering from diabetes and also non-diabetic group.
The time-dependent density functional theory (TDDFT) has been broadly used to investigate the excited-state properties of various molecular systems. However, the current TDDFT heavily relies on outcomes from the corresponding ground-state DFT calculations, which may be prone to errors due to the lack of proper treatment in the non-dynamical correlation effects. Recently, thermally assisted-occupation DFT (TAO-DFT) [J.-D. Chai, J. Chem. Phys. 136, 154104 (2012)], a DFT with fractional orbital occupations, was proposed, explicitly incorporating the non-dynamical correlation effects in the ground-state calculations with low computational complexity. In this work, we develop TDTAO-DFT, which is a TD, linear-response theory for excited states within the framework of TAO-DFT. With tests on the excited states of H2, the first triplet excited state (13Σu+) was described well, with non-imaginary excitation energies. TDTAO-DFT also yields zero singlet-triplet gap in the dissociation limit for the ground singlet (11Σg+) and the first triplet state (13Σu+). In addition, as compared to traditional TDDFT, the overall excited-state potential energy surfaces obtained from TDTAO-DFT are generally improved and better agree with results from the equation-of-motion coupled-cluster singles and doubles.Triplet-triplet annihilation-based photon upconversion (UC) using bulk perovskite sensitizers has been previously shown to facilitate efficient UC at low fluences. However, the fabrication of the UC devices has not been fully optimized; thus, there is room for improvement. Here, we apply techniques that have been successful in enhancing the performance of perovskite solar cells in order to also improve perovskite-sensitized UC devices. In particular, we investigate the use of a post-fabrication thermal annealing step, overstoichiometric vs stoichiometric addition of PbI2 to the perovskite precursors, methylammonium vs formamidinium cation-rich lead halide perovskite compositions, and the use of different solvents for the annihilator molecules on the perovskite/annihilator interface. We find that excess PbI2 does not significantly affect the UC process, while the perovskite composition is crucial for the yield of extracted carriers across the interface. Comparing toluene and chlorobenzene, we find that the solvent used to deposit the annihilator is also a key factor in the overall device performance. Moreover, we find that thermal annealing of the whole device architecture significantly improves the UC performance by a factor of three.In this study, we develop a new approach for stabilization of metallic phases of monolayer MoS2 through the formation of lateral heterostructures composed of semiconducting/metallic MoS2. The structure of metallic (a mixture of T and T') and semiconducting (2H) phases was unambiguously characterized by Raman spectroscopy, x-ray photoelectron spectroscopy, photoluminescence imaging, and transmission electron microscope observations. The amount of NaCl, reaction temperature, reaction time, and locations of substrates are essential for controlling the percentage of metallic/semiconducting phases in lateral heterostructures; loading a large amount of NaCl at low temperatures with short reaction times prefers metallic phases. The existence of the semiconducting phase in MoS2 lateral heterostructures significantly enhances the stability of the metallic phases through passivation of reactive edges. The same approach can be applied to other transition metal dichalcogenides (TMDs), such as WS2, leading to boosting of basic research and application of TMDs in metallic phases.We present an analysis of reported magnetic field effects (MFEs) on the yield of formic acid produced by electrocatalytic reduction of carbon dioxide at a nanoparticle tin electrode [H. P. Pan et al., J. Phys. Chem. Lett. 11, 48-53 (2020)]. Radical pair spin dynamics simulations are used to show that (1) the Δg mechanism favored by Pan et al. is not sufficient to explain the observed magneto-current, (2) field-dependent spin relaxation, resulting from the anisotropy of the g-tensor of CO2•-, combined with the coherent singlet-triplet interconversion arising from isotropic hyperfine and Zeeman interactions, can quantitatively account for the observed MFE, and (3) modification of hyperfine interactions by isotopic substitution (1H → 2H and/or 12C → 13C) could be used to test both the proposed reaction mechanism and the interpretation presented here.Theoretical methods able to screen large sets (e.g., conformers) of possibly large compounds are needed in many typical quantum chemistry applications. For this purpose, we here extend the well-established simplified time-dependent density functional theory (sTD-DFT) method for the calculation of optical rotation. This new scheme is benchmarked against 42 compounds of the OR45 set as well as thirteen helicene derivatives and one bio-molecular system. #link# The sTD-DFT method yields optical rotations in good quantitative agreement with experiment for compounds with a valence-dominated response, e.g., conjugated π-systems, at a small fraction of the computational cost compared to TD-DFT (1-3 orders of magnitude speed-up). For smaller molecules with a Rydberg state dominated response, the agreement between TD-DFT and the simplified version using standard hybrid functionals is somewhat worse but still reasonable for typical applications. Our new implementation in the stda code enables computations for systems with up to 1000 atoms, e.g., for studying flexible bio-molecules.The meta-generalized-gradient approximation (meta-GGA) of the exchange-correlation energy functional can provide appealing performance for the wide range of quantum chemistry and solid-state properties. So far, several meta-GGAs are proposed by fitting to the test sets or/and satisfying as many as known exact constraints. Although the density overlap is treated by meta-GGA functionals efficiently, for non-covalent interactions, a long-range dispersion correction is essential. In this work, we assess the benchmark performance of different variants of the Tao-Mo meta-GGA semilocal functional, i.e., TM [J. Tao and Y. Mo, Phys. Rev. click here , 073001 (2016)] and revTM [S. Jana, K. Sharma, and P. Samal, J. Phys. Chem. A 123, 6356 (2019)], with Grimme's D3 correction for several non-covalent interactions, including hydrogen-bonded systems. link2 We consider the zero, Becke-Johnson (BJ), and optimized power (OP) damping functions within the D3 method with both TM and revTM functionals. It is observed that the overall performance of the functionals gradually improved from zero to BJ and to OP damping. However, the constructed "OP" corrected (rev)TM + D3(OP) functionals perform considerably better compared to other well-known dispersion corrected functionals. Based on the accuracy of the proposed functionals, the future applicability of these methods is also discussed.The H+(CO)2 and D+(CO)2 molecular ions were investigated by infrared spectroscopy in the gas phase and in para-hydrogen matrices. In the gas phase, ions were generated in a supersonic molecular beam by a pulsed electrical discharge. link3 After extraction into a time-of-flight mass spectrometer, the ions were mass selected and probed by infrared laser photodissociation spectroscopy in the 700 cm-1-3500 cm-1 region. Spectra were measured using either argon or neon tagging, as well as tagging with an excess CO molecule. In solid para-hydrogen, ions were generated by electron bombardment of a mixture of CO and hydrogen, and absorption spectra were recorded in the 400 cm-1-4000 cm-1 region with a Fourier-transform infrared spectrometer. A comparison of the measured spectra with the predictions of anharmonic theory at the CCSD(T)/ANO1 level suggests that the predominant isomers formed by either argon tagging or para-hydrogen isolation are higher lying (+7.8 kcal mol-1), less symmetric isomers, and not the global minimum proton-bound dimer. Changing the formation environment or tagging strategy produces other non-centrosymmetric structures, but there is no spectroscopic evidence for the centrosymmetric proton-bound dimer. The formation of higher energy isomers may be caused by a kinetic effect, such as the binding of X (=Ar, Ne, or H2) to H+(CO) prior to the formation of X H+(CO)2. Regardless, there is a strong tendency to produce non-centrosymmetric structures in which HCO+ remains an intact core ion.The synthesis of lanthanide doped up-converting nanoparticles (UCNPs), whose morphological, structural, and luminescence properties are well suited for applications in optoelectronics, forensics, security, or biomedicine, is of tremendous significance. The most commonly used synthesis method comprises decomposition of organometallic compounds in an oxygen-free environment and subsequent infliction of a biocompatible layer on the particle surface. In this work, hydroxyl-carboxyl (-OH/-COOH) type of chelating agents (citric acid and sodium citrate) are used in situ for the solvothermal synthesis of hydrophilic NaY0.5Gd0.3F4Yb,Er UCNPs from rare earth nitrate salts and different fluoride sources (NaF, NH4F, and NH4HF2). X-ray powder diffraction showed crystallization of cubic and hexagonal NaY0.5Gd0.3F4Yb,Er phases in nano- and micro-sized particles, respectively. The content of the hexagonal phase prevails in the samples obtained when Na-citrate is used, while the size and shape of the synthesized mesocrystals are affected by the choice of fluoride source used for precipitation. All particles are functionalized with citrate ligands and emit intense green light at 519 nm and 539 nm (2H11/2, 4S3/2 → 4I15/2) under near infrared light. The intensity of this emission is distressed by the change in the origin of phonon energy of the host matrix revealed by the change in the number of the excitation photons absorbed per emitted photon.Molecular orbital framework is of central importance in chemistry. Often used by chemists and physicists to gain insight into molecular properties, Hartree-Fock or Kohn-Sham orbitals are obtained from rather crude treatments and, strictly speaking, are not observables. Yet, quantum mechanics offers a route for connecting general many-electron wavefunctions with reduced quantities-density matrices and orbitals-which give rise to observable properties. Such mapping makes possible, in principle, reconstruction of these objects from sufficiently detailed experimental data. This Perspective discusses Dyson orbitals and various types of natural transition orbitals and illustrates their role in modeling and interpreting different types of spectroscopic measurements.Constructing matrix product operators (MPOs) is at the core of the modern density matrix renormalization group (DMRG) and its time dependent formulation. For the DMRG to be conveniently used in different problems described by different Hamiltonians, in this work, we propose a new generic algorithm to construct the MPO of an arbitrary operator with a sum-of-products form based on the bipartite graph theory. We show that the method has the following advantages (i) it is automatic in that only the definition of the operator is required; (ii) it is symbolic thus free of any numerical error; (iii) the complementary operator technique can be fully employed so that the resulting MPO is globally optimal for any given order of degrees of freedom; and (iv) the symmetry of the system could be fully employed to reduce the dimension of MPO. To demonstrate the effectiveness of the new algorithm, the MPOs of Hamiltonians ranging from the prototypical spin-boson model and the Holstein model to the more complicated ab initio electronic Hamiltonian and the anharmonic vibrational Hamiltonian with the sextic force field are constructed.
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