A route to high-accuracy ab initio description of electronic excited states in high-spin lanthanide-containing species: A case study of GdO.

Accurate description of electronic excited states of high-spin molecular species is a yet unsolved problem in modern electronic structure theory. A composite computational scheme developed in the present work contributes to solving this task for a challenging case of lanthanide-containing molecules. In the scheme, the highest-spin states whose wavefunctions are dominated by a single Slater determinant are described at the single-reference (SR) CCSD(T) level, whereas the lower-spin states, being inherently multiconfigurational in their nature, are treated with multireference (MR) methods, MRCI and/or CASPT2. An original technique which scales MR results against SR CCSD(T) ones to improve the accuracy in the former is proposed and examined, taking the example of 12 electronic states of gadolinium monoxide, X9Σ-, Y7Σ-, A'9Δ, A1'7Δ, A9Π, A17Π, B9Σ-, B17Σ-, C9Π, C17Π, D9Σ-, and D17Σ-, up to 35 000 cm-1. A multitude of the corresponding Ω (spin-coupled) states was then studied within the state-interacting approach employing the full Breit-Pauli spin-orbit coupling operator with CASSCF-generated ΛS states as a basis. For all ΛS and Ω states, the Gd-O bond lengths, spectroscopic constants ωe, ωexe, αe, and adiabatic excitation energies are obtained. The theoretical predictions are in good agreement with the experimental data, with deviations in excitation energies not exceeding 350 cm-1 (1 kcal/mol). The spectroscopic properties of the yet unobserved electronic states, A'9Δ, A1'7Δ, C9Π, C17Π, D9Σ-, and D17Σ-, are evaluated for the first time.

Indirect bandgap MoSe2 resonators for light-emitting nanophotonics.

Transition metal dichalcogenides (TMDs) are promising for new generation nanophotonics due to their unique optical properties. However, in contrast to direct bandgap TMD monolayers, bulk samples have an indirect bandgap that restricts their application as light emitters. On the other hand, the high refractive index of these materials allows for effective light trapping and the creation of high-Q resonators. In this work, a method for the nanofabrication of microcavities from indirect TMD multilayer flakes, which makes it possible to achieve pronounced resonant photoluminescence enhancement due to the cavity modes, is proposed. Whispering gallery mode (WGM) resonators are fabricated from bulk indirect MoSe2 using resistless scanning probe lithography. A micro-photoluminescence (µ-PL) investigation revealed the WGM spectra of the resonators with an enhancement factor up to 100. The characteristic features of WGMs are clearly seen from the scattering experiments which are in agreement with the results of numerical simulations. It is shown that the PL spectra in the fabricated microcavities are contributed by two mechanisms demonstrating different temperature dependences. The indirect PL, which is quenched with the temperature decrease, and the direct PL which almost does not depend on the temperature. The results of the work show that the suggested approach has great prospects in nanophotonics.

Multi-Frequency Light Sources Based on CVD Diamond Matrices with a Mix of SiV- and GeV- Color Centers and Tungsten Complexes.

Recently, nanodiamonds with negatively charged luminescent color centers based on atoms of the fourth group (SiV-, GeV-) have been proposed for use as biocompatible luminescent markers. Further improvement of the functionality of such systems by expanding the frequencies of the emission can be achieved by the additional formation of luminescent tungsten complexes in the diamond matrix. This paper reports the creation of diamond matrices by a hot filament chemical vapor deposition method, containing combinations of luminescing Si-V and Ge-V color centers and tungsten complexes. The possibility is demonstrated of creating a multicolor light source combining the luminescence of all embedded emitters. The emission properties of tungsten complexes and Si-V and Ge-V color centers in the diamond matrices were investigated, as well as differences in their luminescent properties and electron-phonon interaction at different temperatures.

Creation of Negatively Charged Boron Vacancies in Hexagonal Boron Nitride Crystal by Electron Irradiation and Mechanism of Inhomogeneous Broadening of Boron Vacancy-Related Spin Resonance Lines.

Optically addressable high-spin states (S ≥ 1) of defects in semiconductors are the basis for the development of solid-state quantum technologies. Recently, one such defect has been found in hexagonal boron nitride (hBN) and identified as a negatively charged boron vacancy (VB-). To explore and utilize the properties of this defect, one needs to design a robust way for its creation in an hBN crystal. We investigate the possibility of creating VB- centers in an hBN single crystal by means of irradiation with a high-energy (E = 2 MeV) electron flux. Optical excitation of the irradiated sample induces fluorescence in the near-infrared range together with the electron spin resonance (ESR) spectrum of the triplet centers with a zero-field splitting value of D = 3.6 GHz, manifesting an optically induced population inversion of the ground state spin sublevels. These observations are the signatures of the VB- centers and demonstrate that electron irradiation can be reliably used to create these centers in hBN. Exploration of the VB- spin resonance line shape allowed us to establish the source of the line broadening, which occurs due to the slight deviation in orientation of the two-dimensional B-N atomic plains being exactly parallel relative to each other. The results of the analysis of the broadening mechanism can be used for the crystalline quality control of the 2D materials, using the VB- spin embedded in the hBN as a probe.

State-of-the-art and prospects for intense red radiation from core-shell InGaN/GaN nanorods.

Core-shell nanorods (NRs) with InGaN/GaN quantum wells (QWs) are promising for monolithic white light-emitting diodes and multi-color displays. Such applications, however, are still a challenge because intensity of the red band is too weak compared with blue and green. To clarify this problem, we measured photoluminescence of different NRs, depending on power and temperature, as well as with time resolution. These studies have shown that dominant emission bands come from nonpolar and semipolar QWs, while a broad yellow-red band arises mainly from defects in the GaN core. An emission from polar QWs located at the NR tip is indistinguishable against the background of defect-related luminescence. Our calculations of electromagnetic field distribution inside the NRs show a low density of photon states at the tip, which additionally suppresses the radiation of polar QWs. We propose placing polar QWs inside a cylindrical part of the core, where the density of photon states is higher and the well area is much larger. Such a hybrid design, in which the excess of blue radiation from shell QWs is converted to red radiation in core wells, can help solve the urgent problem of red light for many applications of NRs.

Spectroscopy of YO from first principles.

We report an ab initio study on the spectroscopy of the open-shell diatomic molecule yttrium oxide, YO. The study considers the six lowest doublet states, X2Σ+, A'2Δ, A2Π, B2Σ+, C2Π, D2Σ+, and a few higher-lying quartet states using high levels of electronic structure theory and accurate nuclear motion calculations. The coupled cluster singles, doubles, and perturbative triples, CCSD(T), and multireference configuration interaction (MRCI) methods are employed in conjunction with a relativistic pseudopotential on the yttrium atom and a series of correlation-consistent basis sets ranging in size from triple-ζ to quintuple-ζ quality. Core-valence correlation effects are taken into account and complete basis set limit extrapolation is performed for CCSD(T). Spin-orbit coupling is included through the use of both MRCI state-interaction with spin-orbit (SI-SO) approach and four-component relativistic equation-of-motion CCSD calculations. Using the ab initio data for bond lengths ranging from 1.0 to 2.5 Å, we compute 6 potential energy, 12 spin-orbit, 8 electronic angular momentum, 6 electric dipole moment and 12 transition dipole moment (4 parallel and 8 perpendicular) curves which provide a complete description of the spectroscopy of the system of six lowest doublet states. The Duo nuclear motion program is used to solve the coupled nuclear motion Schrödinger equation for these six electronic states. The spectra of 89Y16O simulated for different temperatures are compared with several available high resolution experimental studies; good agreement is found once minor adjustments are made to the electronic excitation energies.

Unified mechanism of the surface Fermi level pinning in III-As nanowires.

Fermi level pinning at the oxidized (110) surfaces of III-As nanowires (GaAs, InAs, InGaAs, AlGaAs) is studied. Using scanning gradient Kelvin probe microscopy, we show that the Fermi level at oxidized cleavage surfaces of ternary Al x Ga1-x As (0 ≤ x ≤ 0.45) and Ga x In1-x As (0 ≤ x ≤ 1) alloys is pinned at the same position of 4.8 ± 0.1 eV with regard to the vacuum level. The finding implies a unified mechanism of the Fermi level pinning for such surfaces. Further investigation, performed by Raman scattering and photoluminescence spectroscopy, shows that photooxidation of the Al x Ga1-x As and Ga x In1-x As nanowires leads to the accumulation of an excess of arsenic on their crystal surfaces which is accompanied by a strong decrease of the band-edge photoluminescence intensity. We conclude that the surface excess arsenic in crystalline or amorphous forms is responsible for the Fermi level pinning at oxidized (110) surfaces of III-As nanowires.

Toward Chemical Accuracy in ab Initio Thermochemistry and Spectroscopy of Lanthanide Compounds: Assessing Core-Valence Correlation, Second-Order Spin-Orbit Coupling, and Higher Order Effects in Lanthanide Diatomics.

The higher order (HO) correlation beyond the coupled-cluster single double (triple) CCSD(T) level of theory, second-order spin-orbit coupling (SOC), and core-valence (CV) correlation effects on bond length, re, vibrational frequency, ωe, and dissociation energy, De, are studied for a set of 17 lanthanide containing diatomics, including lanthanum, europium, ytterbium, and lutetium oxides and halides. Convergence in the magnitudes of the SOC, CV, and HO corrections with respect to basis set size is examined using a sequence of double, triple, and quadruple-ζ basis sets, with the complete basis set (CBS) limit estimates provided in most cases. The CV effects on De, re, and ωe are calculated to amount up to 1.3 kcal·mol-1, 0.008 Å, and 5 cm-1, respectively. A detailed analysis of the origin of the CV effect with a particular accounting for various subvalence shells reveals that, generally, the Ln 4d correlation makes a major contribution, although in some instances the lower-lying 4sp shells contribute largely and even more substantially than 4d. The second-order SOC effect evaluated via two-component and four-component relativistic techniques proves to be non-negligible, especially for heavier species, e.g., LaI, in which it is as large as 0.8 kcal·mol-1 in De, 0.002 Å in re, and 1.3 cm-1 in ωe. Higher order correlation effects assessed through the CCSDT(Q) level are mostly less than 0.8 kcal·mol-1, 0.004 Å, and 5 cm-1; however, in species with prominence of nondynamical correlation, e.g., EuO, YbF, and LuO, the HO correction can amount to 1.2-1.6 kcal·mol-1, 0.005-0.008 Å, and 8-30 cm-1 in De, re, and ωe, respectively. In general, the [CCSD(T)+CV]/CBS + SOC + HO composite results are in good agreement with the available experimental data, exhibiting a mean absolute deviation of 1.8 kcal·mol-1 in De, 0.0023 Å in re, and 3.5 cm-1 in ωe. A significant experimental outlier, the bond length in YbI, is revealed, implying the need for re-examination of the experimental data.

Low-strain heteroepitaxial nanodiamonds: fabrication and photoluminescence of silicon-vacancy colour centres.

Nanodiamonds with the 'diamond' 1332.5 cm(-1) Raman line as narrow as 1.8 cm(-1) have been produced by reactive ion etching in oxygen plasma of heteroepitaxial diamond particles grown by microwave plasma enhanced chemical vapour deposition (MWPECVD) on silicon. After the etching, a doublet is recorded in the zero-phonon line photoluminescence spectra of an ensemble of silicon-vacancy (SiV) centres at 10 K. Each line of the doublet is split into two lines corresponding to the optical transitions between the split excited and ground energy levels of the SiV centres. These Raman and photoluminescent features have been observed previously only in low-strain homoepitaxial diamond films and single-crystal diamond.

Composite vibrational spectroscopy of the group 12 difluorides: ZnF2, CdF2, and HgF2.

The vibrational spectra of group 12 difluorides, MF2 (M = Zn, Cd, Hg), were investigated via coupled cluster singles, doubles, and perturbative triples, CCSD(T), including core correlation, with a series of correlation consistent basis sets ranging in size from triple-zeta through quintuple-zeta quality, which were then extrapolated to the complete basis set (CBS) limit using a variety of extrapolation procedures. The explicitly correlated coupled cluster method, CCSD(T)-F12b, was employed as well. Although exhibiting quite different convergence behavior, the F12b method yielded the CBS limit estimates closely matching more computationally expensive conventional CBS extrapolations. The convergence with respect to basis set size was examined for the contributions entering into composite vibrational spectroscopy, including those from higher-order correlation accounted for through the CCSDT(Q) level of theory, second-order spin-orbit coupling effects assessed within four-component and two-component relativistic formalisms, and vibrational anharmonicity evaluated via a perturbative treatment. Overall, the composite results are in excellent agreement with available experimental values, except for the CdF2 bond-stretching frequencies compared to spectral assignments proposed in a matrix isolation infrared and Raman study of cadmium difluoride vapor species [Loewenschuss et al., J. Chem. Phys. 50, 2502 (1969); Givan and Loewenschuss, J. Chem. Phys. 72, 3809 (1980)]. These assignments are called into question in the light of the composite results.

Influence of Substrate Microstructure on the Transport Properties of CVD-Graphene.

We report the study of electrical transport in few-layered CVD-graphene located on nanostructured surfaces in view of its potential application as a transparent contact to optoelectronic devices. Two specific surfaces with a different characteristic feature scale are analyzed: semiconductor micropyramids covered with SiO2 layer and opal structures composed of SiO2 nanospheres. Scanning tunneling microscopy (STM) and scanning electron microscopy (SEM), as well as Raman spectroscopy, have been used to determine graphene/substrate surface profile. The graphene transfer on the opal face centered cubic arrangement of spheres with a diameter of 230 nm leads to graphene corrugation (graphene partially reproduces the opal surface profile). This structure results in a reduction by more than 3 times of the graphene sheet conductivity compared to the conductivity of reference graphene located on a planar SiO2 surface but does not affect the contact resistance to graphene. The graphene transfer onto an organized array of micropyramids results in a graphene suspension. Unlike opal, the graphene suspension on pyramids leads to a reduction of both the contact resistance and the sheet resistance of graphene compared to resistance of the reference graphene/flat SiO2 sample. The sample annealing is favorable to improve the contact resistance to CVD-graphene; however, it leads to the increase of its sheet resistance.

Benzimidazoles and benzoxazoles via the nucleophilic addition of anilines to nitroalkanes.

PPA-induced umpolung triggers efficient nucleophilic addition of unactivated anilines to nitroalkanes to produce N-hydroxyimidamides. The latter undergo sequential acid-promoted cyclocondensation with ortho-OH or ortho-NHR moieties to afford benzoxazoles and benzimidazoles, respectively.

Activity of 2-aryl-2-(3-indolyl)acetohydroxamates against drug-resistant cancer cells.

Many types of tumor, including glioma, melanoma, non-small cell lung, esophageal, and head and neck cancer, among others, are intrinsically resistant to apoptosis induction and poorly responsive to current therapies with proapoptotic agents. In addition, tumors often develop multidrug resistance based on the cellular efflux of chemotherapeutic agents. Thus, novel anticancer agents capable of overcoming these intrinsic or developed tumor resistance mechanisms are urgently needed. We describe a series of 2-aryl-2-(3-indolyl)acetohydroxamic acids that are active against apoptosis- and multidrug-resistant cancer cells as well as glioblastoma neurosphere stemlike cell cultures derived from patients. Thus, the described compounds serve as a novel chemical scaffold for the development of potentially highly effective clinical cancer drugs.

Highly efficient modular metal-free synthesis of 3-substituted 2-quinolones.

A modular approach to 3-substituted 2-quinolones via a cascade annulation reaction between 4-nitroketones and hydrazines has been developed.

Metal-free transannulation reaction of indoles with nitrostyrenes: a simple practical synthesis of 3-substituted 2-quinolones.

3-Substituted 2-quinolones are obtained via a novel, metal-free transannulation reaction of 2-substituted indoles with 2-nitroalkenes in polyphosphoric acid. The reaction can be used in conjunction with the Fisher indole synthesis offering a practical three-component heteroannulation methodology to produce 2-quinolones from arylhydrazines, 2-nitroalkenes and acetophenone.

Lipid regulators during atherogenesis: expression of LXR, PPAR, and SREBP mRNA in the human aorta.

Transcription factors LXRs, PPARs, and SREBPs have been implicated in a multitude of physiological and pathological processes including atherogenesis. However, little is known about the regulation of these transcription factors at different stages of atherosclerosis progression. Quantitative real-time polymerase chain reaction (qRT-PCR) was used to compare the contents of mRNAs in pairs intact-injured aorta fragments taken from the same donors. Only minor changes in LXRα, LXRß, PPARα, PPARγ, SREBP1, and SREBP2 mRNA levels were found in initial lesions as compared with intact non-diseased tissue. The contents of all mRNAs but SREBP2 mRNA were found to be progressively up-regulated in fatty streaks and fibrous lipoid plaques. These changes were only partially reproduced in cultured macrophages upon lipid loading. Wave-shaped changes in abundance of correlations between given group of mRNAs and 28 atherosclerosis-related mRNA species in the course of atherogenesis were observed. The impact of specific mRNA correlations on the total correlations also significantly varied between different lesion types. The study suggests that the extent and forms of LXR/PPAR/SREBP participation in intima functions vary nonlinear in individual fashion in atherogenesis. We speculate that the observed changes in mRNAs expression and coupling reflect shifts in lipid ligands availability and cellular composition in the course of atherosclerosis progression.

Changes of lysosomes in the earliest stages of the development of atherosclerosis.

One of hypotheses of atherosclerosis is based on a presumption that the zones prone to the development of atherosclerosis contain lysosomes which are characterized by enzyme deficiency and thus, are unable to dispose of lipoproteins. The present study was undertaken to investigate the characteristics and changes of lysosomes in the earliest stages of the development of atherosclerosis. Electron microscopic immunocytochemistry revealed that there were certain changes in the distribution of CD68 antigen in lysosomes along the 'normal intima-initial lesion-fatty streak' sequence. There were no significant changes found in the key mRNAs encoding for the components of endosome/lysosome compartment in initial atherosclerotic lesions, but in fatty streaks, the contents of EEA1 and Rab5a mRNAs were found to be diminished while the contents of CD68 and p62 mRNAs were increased, compared with the intact tissue. The study reinforces a view that changes occurring in lysosomes play a role in atherogenesis from the very earlier stages of the disease.

3- and 19-oximes of 16alpha,17alpha-cyclohexanoprogesterone derivatives: synthesis and interactions with progesterone receptor and other proteins.

Series of 3- and 19-oximes of 16alpha,17alpha-cyclohexanoprogesterone derivatives (pregna-d'-pentaranes) have been synthesized with the aim of probing the surfaces of progesterone receptor's and two other protein ligand binding pockets neighboring to 3- and 19-positions of steroid core. The same derivatives were also studied as possible intermediates for attachment to matrixes. The data on affinity constants suggest the presence of hydrophobic cavities with hydrophilic necks in the progesterone receptor and serum pentaranophylin near C19 of bound ligand and the lack of such a cavity in uterine pentaranophylin. Any of 3-oxime substitutions were found to significantly diminish the ligand affinity for the progesterone receptor. It was also found that some of these modifications, in the Z-configuration particularly, might increase the affinity for serum and uterine pentaranophylins. The latter finding suggests the presence of large cavities near C3 of bound ligand in these proteins and interchangeability between 3-keto and 3-oxime groups in ligand-protein interactions.