Row Elements Research Articles

Alternate formation of AlOH from third row diatomic hydrides and oxides

One of the most abundant Al-containing molecules detected in the interstellar medium (ISM) is AlOH. Over the past several years, there have been various pathways proposed for the formation of AlOH in the ISM, including reactions between AlO and H2 or H2O. However, these pathways include an energetic barrier from a transition state that likely prevents the reaction from progressing efficiently in the low temperature/low pressure environment of the ISM. Recently, a barrierless pathway for formation of AlOH from AlO and AlH has been proposed for the formation of AlOH. Even so, only one of these species really needs to contain an aluminum atom. To account for this, alternative but related pathways reacting the known interstellar molecule AlO with XH and AlH with XO (X = Mg, Si, P, or S) to form AlOH are explored with high accuracy quantum chemical calculations via CCSD(T)-F12b/cc-pVTZ-F12. Each third row element has at least one pair of reactants that lead to exothermic formation of AlOH. These reactions can go on to form other aluminum oxides and aluminum oxide clusters that may, in part, lead to the formation of interstellar dust grains.

Probing 4 × 4 quark mixing matrix

Without adhering to any specific model, we have presented 4 [Formula: see text] 4 quark mixing matrix as an extension of the 3 [Formula: see text] 3 Particle Data Group (PDG) parametrization of the Cabibbo–Kobayashi–Maskawa (CKM) matrix Using unitarity constraints as well as the hierarchy among the elements of the 3 [Formula: see text] 3 CKM matrix, we have found the hierarchy among the fourth row and fourth column elements of the 4 [Formula: see text] 4 quark mixing matrix. Further, for the fourth generation case, we have explicitly found the nine independent rephasing invariant parameters [Formula: see text]. Also, using phenomenological estimates of the fourth row and fourth column elements, we have numerically evaluated these nine parameters.

Performance assessment of the effective core potentials under the fermionic neural network: First and second row elements.

The rapid development of deep learning techniques has driven the emergence of a neural network-based variational Monte Carlo (VMC) method (referred to as FermiNet), which has manifested high accuracy and strong predictive power in the electronic structure calculations of atoms, molecules, and some periodic systems. Recently, the implementation of the effective core potential (ECP) scheme has further facilitated more efficient calculations in practice. However, there is still a lack of comprehensive assessments of the ECP's performance under the FermiNet. In this work, we set sail to fill this gap by conducting extensive tests on the first two row elements regarding their atomic, spectral, and molecular properties. Our major finding is that, in general, the qualities of ECPs have been correctly reflected under FermiNet. Two recently built ECP tables, namely, correlation consistent ECP (ccECP) and energy consistent correlated electron pseudopotential (eCEPP), seem to prevail in terms of overall performance. In particular, ccECP performs slightly better on spectral precision and covers more elements, while eCEPP is more systematically built from both shape and energy consistency and better treats the core polarization. On the other hand, the high accuracy of the all-electron calculations is hindered by the absence of relativistic effects as well as the numerical instabilities in some heavier elements. Finally, with further in-depth discussions, we generate possible directions for developing and improving FermiNet in the near future.

Interstage flow matrices: Population statistic derived from matrix population models

Abstract Many population statistics describe the characteristics of populations within and among species. These are useful for describing population dynamics, understanding how environmental factors alter demographic patterns, testing hypotheses related to the evolution of life history characteristics and informing the effective management of populations. In this study, we propose a population statistic: the interstage flow. The interstage flow is defined as the product of the element in the ith row, the jth column of the population projection matrix and the jth element of the normalized stable stage distribution. The sum of the interstage flow matrix elements is equal to the population growth rate (PGR), which is the dominant eigenvalue of the population projection matrix. The interstage flow matrix elements allow decomposition of PGR into component contributions made by transitions between developmental stages. We demonstrate the utility of interstage flow matrices using matrix population models from the COMPADRE plant matrix database. We compared interstage flows among four life history/functional groups (FGs) (semelparous herbs, iteroparous herbs, shrubs and trees) and described how PGR reflected individual transitions related to stasis, fecundity and growth. We found that the individual flows are different among FGs. Synthesis. The proposed population statistic, the interstage flow matrix, describes the contribution of individual developmental stage transitions to the PGR. The flow of individuals between developmental stages differs in distinctive ways among different life histories and FGs. The interstage flow matrix is a valuable statistic for describing these differences.

Developing correlation-consistent numeric atom-centered orbital basis sets for krypton: Applications in RPA-based correlated calculations.

Localized atomic orbitals are the preferred basis set choice for large-scale explicit correlated calculations, and high-quality hierarchical correlation-consistent basis sets are a prerequisite for correlated methods to deliver numerically reliable results. At present, numeric atom-centered orbital (NAO) basis sets with valence correlation consistency (VCC), designated as NAO-VCC-nZ, are only available for light elements from hydrogen (H) to argon (Ar) [Zhang et al., New J. Phys. 15, 123033 (2013)]. In this work, we extend this series by developing NAO-VCC-nZ basis sets for krypton (Kr), a prototypical element in the fourth row of the periodic table. We demonstrate that NAO-VCC-nZ basis sets facilitate the convergence of electronic total-energy calculations using the Random Phase Approximation (RPA), which can be used together with a two-point extrapolation scheme to approach the complete basis set limit. Notably, the Basis Set Superposition Error (BSSE) associated with the newly generated NAO basis sets is minimal, making them suitable for applications where BSSE correction is either cumbersome or impractical to do. After confirming the reliability of NAO basis sets for Kr, we proceed to calculate the Helmholtz free energy for Kr crystal at the theoretical level of RPA plus renormalized single excitation correction. From this, we derive the pressure-volume (P-V) diagram, which shows excellent agreement with the latest experimental data. Our work demonstrates the capability of correlation-consistent NAO basis sets for heavy elements, paving the way toward numerically reliable correlated calculations for bulk materials.

Fourier-Based Fast 3-D Ultrasound Imaging Using Row-Column-Addressed 2-D Arrays.

A Fourier-based fast 3-D ultrasound imaging method using row-column-addressed (RCA) 2-D arrays is presented. The row elements in an RCA array are activated sequentially, and all the column elements are used to receive. The obtained dataset is adapted to approximate to that obtained using a fully sampled array after a plane wave at a given incident angle is transmitted. In this way, the fast algorithm in plane-wave Fourier imaging (PWFI) can be applied to the adapted dataset. In addition, synthesizing multiple datasets based on multiple incident angles enables angular compounding, which improves the image quality. The proposed method was validated using computer simulations and physical-phantom experiments. The results show that the spatial resolution and contrast of the proposed method are comparable with those of its PWFI counterpart without requiring a fully sampled (FS) array. Compared with the delay-and-sum (DAS) method using the RCA array, the proposed method provides comparable spatial resolution but lower contrast; however, the computational complexity is significantly reduced from O(N4Nz) to O(WN2Nz log2(N2Nz)) , where N is the number of elements on each side of the RCA array, Nz is the number of voxels in the axial direction in the output image, and W is the number of compounding angles. For example, in the simulated results when the maximum compounding angle M is 5°, at a given point the lateral - 6-dB width provided by the proposed method is 0.241 mm (0.267 mm for DAS), the contrast ratio of a hyperechoic cyst is 8.87 dB (9.10 dB for DAS), the number of real number operations is reduced by a factor of 20.62, and the number of memory accesses is reduced by a factor of 47.21, both compared with DAS. This novel fast algorithm could facilitate the development of compact real-time 3-D imaging systems, especially when the channel count is high and a large field of view (FOV) is required.

Angle-strained sila-cycloalkynes.

Second row elements in small- and medium-rings modulate strain. Herein we report the synthesis of two novel oligosilyl-containing cycloalkynes that exhibit angle-strain, as observed by X-ray crystallography. However, the angle-strained sila-cyclooctynes are sluggish participants in cycloadditions with benzyl azide. A distortion-interaction model analysis based on density functional theory calculations was performed.

CO oxidation reactions on 3-d single metal atom catalysts/MgO(100).

The present work deals with a comprehensive computational theoretical study of the molecular CO and O2 adsorption on 3d single atoms (M/MgO(100)). The study is based on the chemical elements of the 3d row, as they represent an economic advantage compared with the so-called noble metals. The present study has been performed employing density functional theory calculations. Through the representation of the metastable states, we perform a synergetic analysis of the CO oxidation reaction to find trends that suggest the possible use of new candidates such as Ni/MgO(100) or Cu/MgO(100) single-atom catalysts, for this type of redox reaction. We found that Ni and Cu produce energetically viable CO to CO2 reactions. Ni and Cu atoms show the greatest diffusion barrier and are the best candidates due to their low sintering capability. The energetic and electronic properties of the single Cu and Ni atoms on MgO (100) give them the best characteristics to help in the CO oxidation process.

Planar tetracoordinate fluorine atom: global minimum with viable possibility.

Planar hypercoordinate structures are emerging tremendously. Most of the second-row elements from the periodic table exhibit this remarkable structural feature. Planar tetracoordinate fluorine (ptF) atoms were also predicted in group 13 supported clusters. However, high-level ab initio calculations nullified the fact and established that all these ptFs were not minimum energy structures on the potential energy surface. Thus, a true ptF is still scarce in the literature. Herein, we propose the unprecedented ptF as the global minimum of the C2V symmetric H3Li4F- cluster. Heavier alkali metals (Na and K) showed similar results. Both density functional theory (DFT) and ab initio calculations revealed that the ptF structure is a real minimum and indeed, the global minimum. Bonding analysis indicates that the central fluorine atom is stabilized by multicentre bonding with four surrounding Li atoms. Natural charge analysis reveals that the fluorine atom is negatively charged, which is strongly attracted by the positively charged surrounding lithium centres, thereby imparting significant electrostatic attraction. Aromaticity has no role to play here. The cluster is dynamically stable and is expected to be detected in the gas phase.

The p-block challenge: assessing quantum chemistry methods for inorganic heterocycle dimerizations.

The elements of the p-block of the periodic table are of high interest in various chemical and technical applications like frustrated Lewis-pairs (FLP) or opto-electronics. However, high-quality benchmark data to assess approximate density functional theory (DFT) for their theoretical description are sparse. In this work, we present a benchmark set of 604 dimerization energies of 302 "inorganic benzenes" composed of all non-carbon p-block elements of main groups III to VI up to polonium. This so-called IHD302 test set comprises two classes of structures formed by covalent bonding and by weaker donor-acceptor (WDA) interactions, respectively. Generating reliable reference data with ab initio methods is challenging due to large electron correlation contributions, core-valence correlation effects, and especially the slow basis set convergence. To compute reference values for these dimerization reactions, after thorough testing, we applied a computational protocol using state-of-the-art explicitly correlated local coupled cluster theory termed PNO-LCCSD(T)-F12/cc-VTZ-PP-F12(corr.). It includes a basis set correction at the PNO-LMP2-F12/aug-cc-pwCVTZ level. Based on these reference data, we assess 26 DFT methods in combination with three different dispersion corrections and the def2-QZVPP basis set, five composite DFT approaches, and five semi-empirical quantum mechanical methods. For the covalent dimerizations, the r2SCAN-D4 meta-GGA, the r2SCAN0-D4 and ωB97M-V hybrids, and the revDSD-PBEP86-D4 double-hybrid functional are found to be the best-performing methods among the evaluated functionals of the respective class. However, since def2 basis sets for the 4th period are not associated to relativistic pseudo-potentials, we obtained significant errors in the covalent dimerization energies (up to 6 kcal mol-1) for molecules containing p-block elements of the 4th period. Significant improvements were achieved for systems containing 4th row elements by using ECP10MDF pseudopotentials along with re-contracted aug-cc-pVQZ-PP-KS basis sets introduced in this work with the contraction coefficients taken from atomic DFT (PBE0) calculations. Overall, the IHD302 set represents a challenge to contemporary quantum chemical methods. This is due to a large number of spatially close p-element bonds which are underrepresented in other benchmark sets, and the partial covalent bonding character for the WDA interactions. The IHD302 set may be helpful to develop more robust and transferable approximate quantum chemical methods in the future.

On the Efficiency of the Density Functional Theory (DFT)-Based Computational Protocol for 1H and 13C Nuclear Magnetic Resonance (NMR) Chemical Shifts of Natural Products: Studying the Accuracy of the pecS-n (n = 1, 2) Basis Sets.

The basis set issue has always been one of the most important factors of accuracy in the quantum chemical calculations of NMR chemical shifts. In a previous paper, we developed new pecS-n (n = 1, 2) basis sets purposed for the calculations of the NMR chemical shifts of the nuclei of the most popular NMR-active isotopes of 1-2 row elements and successfully approbated these on the DFT calculations of chemical shifts in a limited series of small molecules. In this paper, we demonstrate the performance of the pecS-n (n = 1, 2) basis sets on the calculations of as much as 713 1H and 767 13C chemical shifts of 23 biologically active natural products with complicated stereochemical structures, carried out using the GIAO-DFT(PBE0) approach. We also proposed new alternative contraction schemes for our basis sets characterized by less contraction depth of the p-shell. New contraction coefficients have been optimized with the property-energy consistent (PEC) method. The accuracies of the pecS-n (n = 1, 2) basis sets of both the original and newly contracted forms were assessed on massive benchmark calculations of proton and carbon chemical shifts of a vast variety of natural products. It was found that less contracted pecS-n (n = 1, 2) basis sets provide no noticeable improvement in accuracy. These calculations represent the most austere test of our basis sets as applied to routine calculations of the NMR chemical shifts of real-life compounds.

Theoretical predictions of properties and adsorption behavior of group 1 and 2 elements, including elements 119 and 120, on the surface of gold from periodic DFT calculations

Properties of group 1 and 2 elements and their (oxy)hydrides, including those of elements 119 and 120, adsorbed on the gold (111) surface were calculated using the AMS ADF and periodic BAND software. The results show that all the group 1 elements’ species should adsorb well on the surface of gold, with the following sequence in the adsorption strength MH > M > MOH. The species of elements 119 and 120 should adsorb most weakly in group 1 and 2, respectively, due to the strong relativistic stabilisation of the 8s AO. A reversal of trends in the adsorption energies, E ads, and other properties is established in group 1 and 2 from the elements of the 6th row, Cs and Ba, respectively, due to reversal in the energies and space distribution of the ns AO. The latter is caused by the relativistic stabilisation and contraction of the ns AOs. The obtained E ads values of the group 1 and 2 elements and their compounds, above 180 kJ/mol, mean that very high temperatures of the gas phase chromatography column with gold plated detectors are required to observe an adsorption equilibrium, i.e. a peak of the distribution of decay events in the column.

Compressed channel estimation for RIS-assisted wireless systems: An efficient sparse recovery algorithm

The reconfigurable intelligent surface (RIS) technology plays an essential role in controlling the propagation environment of wireless systems, specifically millimeter wave (mmWave) communication systems. However, a considerable number of pilot signals should be provided at the base station (BS) side for channel estimation due to the significant passive elements installed in the RIS. In this paper, we propose a novel sparse recovery algorithm by exploiting the row, common, and individual sparse elements of the channel in a new way. Furthermore, as an essential presumption of real environments, a sparse channel with unknown parameters is considered. Then a halting method is introduced to stop the proposed algorithm at the best time. The numerical results demonstrate that the proposed algorithm can alleviate the pilot overhead problem substantially while the mean square error (MSE) still approaches the performance bound.

A comparison of latent semantic analysis and correspondence analysis of document-term matrices

Abstract Latent semantic analysis (LSA) and correspondence analysis (CA) are two techniques that use a singular value decomposition for dimensionality reduction. LSA has been extensively used to obtain low-dimensional representations that capture relationships among documents and terms. In this article, we present a theoretical analysis and comparison of the two techniques in the context of document-term matrices. We show that CA has some attractive properties as compared to LSA, for instance that effects of margins, that is, sums of row elements and column elements, arising from differing document lengths and term frequencies are effectively eliminated so that the CA solution is optimally suited to focus on relationships among documents and terms. A unifying framework is proposed that includes both CA and LSA as special cases. We empirically compare CA to various LSA-based methods on text categorization in English and authorship attribution on historical Dutch texts and find that CA performs significantly better. We also apply CA to a long-standing question regarding the authorship of the Dutch national anthem Wilhelmus and provide further support that it can be attributed to the author Datheen, among several contenders.

All-electron ZORA triple zeta basis sets for the elements Cs–La and Hf–Rn

Segmented all-electron basis set of triple zeta valence quality plus polarization functions (TZP) for the elements of the fifth row to be used together with the zero-order regular approximation (ZORA) is carefully constructed. To correctly describe electrons distant from atomic nuclei, the basis set is augmented with diffuse functions giving rise to a set designated as ATZP-ZORA. At the ZORA-B3LYP theoretical level, these sets are used to calculate the ionization energy and mean dipole polarizability of some atoms, bond length, dissociation energy, and harmonic vibrational frequency of diatomic molecules. Then, these results are compared with the theoretical and experimental data found in the literature. Even considering that our sets are relatively compact, they are sufficiently accurate and reliable to perform property calculations involving simultaneously electrons from the inner shell and outer shell. The performances of the ZORA and second-order Douglas–Kroll–Hess Hamiltonians are evaluated and the results are also discussed.

Heat Transfer Slot Matrix for Compact Rotary Heat Exchangers with Ultra-High Regeneration Ratio for Microturbines

This paper considers the problem of the influence of distancing elements in slot matrix channels on the thermohydraulic characteristics of the matrix of a rotary heat exchanger having various values of the height of the slot channels. The following tasks were carried out: mathematical modeling of thermohydraulic processes in different slot channels having constant height along them (from 0.3 mm to 0.5 mm); analysis of the influence of the slit channels' height, the number of distancing elements in rows, the distance between rows and the total number of elements on the average value of the Nusselt number and on the pressure drop; analysis of the effect of changes in speed and temperature conditions on thermal and hydraulic characteristics. The most important results are the following facts: the influence of the relative location of the distancing elements on the thermohydraulic characteristics of the flow is negligible; changes in the temperature and speed regime of the laminar flow practically does not affect the intensity of convection in the matrix channels; an increase in the height of the slot channel leads to a relatively small decrease in the average value of the Nusselt number. The significance of the results obtained is that they can be the basis for adjusting the methods of design calculations of rotary heat exchangers taking into account the decrease in thermal efficiency caused by the presence of distancing elements in the channels of their matrices. Recommendations can be made to minimize the number of distancing elements without considering their mutual location.

Active Thermochemical Tables: Enthalpies of Formation of Bromo- and Iodo-Methanes, Ethenes and Ethynes

The thermochemistry of halocarbon species containing iodine and bromine is examined through an extensive interplay between new Feller-Peterson-Dixon (FPD) style composite methods and a detailed analysis of all available experimental and theoretical determinations using the thermochemical network that underlies the Active Thermochemical Tables (ATcT). From the computational viewpoint, a slower convergence of the components of composite thermochemistry methods is observed relative to species that solely contain first row elements, leading to a higher computational expense for achieving comparable levels of accuracy. Potential systematic sources of computational uncertainty are investigated, and, not surprisingly, spin-orbit coupling is found to be a critical component, particularly for iodine containing molecular species. The ATcT analysis of available experimental and theoretical determinations indicates that prior theoretical determinations have significantly larger uncertainties than originally reported, particularly in cases where molecular spin-orbit effects were ignored. Accurate and reliable heats of formation are reported for 38 halogen containing systems, based on combining the current computations with previous experimental and theoretical work via the ATcT approach.

Three-dimensional ultrafast ultrasound imaging of blood flow using row-column addressing array: A simulation study

Three-dimensional (3D) ultrafast imaging is important for ultrasound technology development. The traditional 3D imaging method based on fully sampled two-dimensional (2D) matrix often requires a large number of electronic channels with high density which limits the aperture size and imaging resolution in application. Recently developed row-column addressing (RCA) matrix effectively reduces the number of electronic channels from <i>N</i> × <i>N</i> to <i>N</i> + <i>N</i> by addressing the row and column elements. The beamforming strategy designed for 3D ultrasound imaging was based on the coherent compounding of orthogonal plane waves (OPW). Such a multi-angle OPW compounding strategy achieves virtual transmit focusing in both directions by transmitting a set of plane waves in one direction and receiving along the orthogonal direction, which finally leads to an isotropic point spread function (PSF). In this paper, multi-angle OPW method was investigated for 3D blood flow imaging using an RCA matrix with 128 rows and 128 columns, centered at 6 MHz. The delay and sum (DAS) beamforming was developed for coherent OPW compounding, and the singular value decomposition (SVD) filtering method was used for separating the dynamic blood flow signals from the static tissue signals and low-amplitude noise. The Doppler velocity was computed by the autocorrelation method, and finally the 3D power Doppler and color Doppler imaging of the blood flow were realized. To evaluate the imaging quality and investigate the effect of different OPW tilting angles, quantitative analysis was carried out using multiple parameters, including –6 dB resolution measurements of the PSF, SNR of the power Doppler images and velocity distribution of the color Doppler. The –6 dB resolution is improved from 0.986 mm to 0.493 mm with the number of angles increasing from 5 to 33. With 17 plane wave angles, the SNR of the power Doppler image reaches 30 dB, and the average deviation between the velocity distribution along the diameter of the blood flow phantom and the actual value is about 26.0%. In conclusion, results show that the ultrafast 3D imaging method based on RCA matrix can obtain 3D B-mode, power Doppler and color Doppler images. Increasing the number of tilting angles and enlarging the angle range can significantly improve the imaging quality. The proposed method can be helpful for developing 3D ultrafast ultrasound Doppler imaging and functional ultrasound imaging based on neuro-vascular coupling.

МЕТОД КОДОВОЇ ЛІНІЙНОЇ ІНТЕРПОЛЯЦІЇ ДЛЯ ФОРМУВАННЯ ВІДРІЗКІВ ПРЯМИХ

Graphic images are formed using graphic primitives. These are the smallest, indivisible from the point of view of application programs, graphic elements used as the basis for building more complex images. Among the graphic primitives, the segments of straight lines, for the formation of which provides linear interpolation, have the highest specific weight. The performance of forming a graphic scene depends on the time of vector generation, therefore the question of increasing the performance of linear interpolation is relevant, especially for dynamic images. With the use of matrix screens and matrix executive bodies in registration devices, the possibility of one-stroke reproduction of row or column elements appears, which allows you to significantly increase the speed of these devices. This mode of operation is promising. Its organization requires the development of interpolation methods that allow in one interpolation cycle to receive the increment code in a row or column (code interpolation). A coded linear interpolation method is proposed, the feature of which is determined in each interpolation clock of digital segments, which includes the number of increments of the same type with the same ordinate (abscissa). For this cycle, prepare for interpolation a larger increment of the line segment to a smaller one. In the future, this ratio and the remainder of the division are used to determine digital segments. In the proposed method, the remainder of the division of a larger increment by a smaller one is accumulated, which is equal to the smaller increment. This allows you to eliminate the accumulation of error and ensure that the end point of the straight line segment is reached. The maximum interpolation error in this case does not exceed half of the discretization step, which is due to the symmetry of the error. The code linear interpolation algorithm is proposed. The research carried out in the work can be used to build high-performance computer graphics tools.

Non-linear averaging-based operators of pseudo-hesitant fuzzy elements and an application

Data modeling/aggregating, in many uncertain real-world' problems such as decision-making processes, has gotten more attention in recent years. Due to a variety of uncertainty sources, various types of fuzzy sets, and various types of averaging-based aggregation functions have been proposed. The power average operator (PAO), as a nonlinear operator, is more appropriate than other averaging-based functions for situations where different values are given on a single subject. In this paper, PAO will be extended to be used in the aggregation process of given pseudo-hesitant fuzzy elements (pseudo-HFEs), and some needed properties have been discussed, too. Then, four kinds of PAO with pseudo-HFEs, i.e., power average operator of pseudo-HFEs, power weighted average operator of pseudo-HFEs, power ordered weighted average operator of pseudo-HFEs and power hybrid average operator of pseudo-HFEs, will be defined. To solve a multi-attribute group decision-making (MAGDM) problem, the evaluation step done by both decision-makers and self-assessment will be quantified by pseudo-HFEs. Then the PAO will be applied to aggregate the row elements of the resulting decision matrix. The ranking orders of obtained pseudo-HFEs, show the options' orders. Finally, the proposed method will be used to solve a multi-attribute group decision-making problem, illustrated numerically, analyzed, and validated.