Ab Initio Calculations Research Articles

Formation of homogeneous pyridinic emission states in carbon dots via solid-state carbonization of aminoquinoline: Optical design principles and light-emitting diode applications

Developing carbon dots (CDs) for practical applications faces significant hurdles due to non-homogeneity in their chemical structure, leading to broad spectral distribution and the excitation-energy-dependent behavior of their fluorescence (FL) emission properties. To address this challenge, we implemented solid-state carbonization of 6-aminoquinoline (6-AQ) devoid of any additives that could induce chemical non-homogeneity. This process yielded pyridinic-nitrogen-doped CDs (PN-CDs) characterized by homogenous, uniform emission states arising from pyridine-incorporated heteroatomic structures. Notably, these PN-CDs exhibited excitation-energy-independent FL at 520 nm with a full-width-half-maximum of 70 nm. To elucidate the structure-property relationship in PN-CDs, a comprehensive analysis encompassing time-resolved spectroscopy and ab initio calculations was conducted. Furthermore, we performed a comparative study by manipulating synthesis parameters and utilizing six AQ isomers, offering valuable insights to optimize the optical properties of PN-CDs. Finally, we successfully demonstrated high-color-purity and efficient green light-emitting diodes utilizing PN-CDs, highlighting their potential for future display applications. This paves the way for advancement in optical materials with enhanced performance and reduced environmental impact.

Unveiling the organic acids with auxiliary functional groups effect on α‐hemihydrate gypsum: Ab initio calculations

AbstractRegulating the crystal morphology of low aspect ratio, short columnar α‐hemihydrate gypsum (α‐HH) is crucial due to its distinctive physical and chemical properties, which make it widely applicable. In this work, succinic acid, malic acid, and maleic acid were selected as the research objects, among which the number and spacing of carboxyl groups were the same, while the auxiliary functional groups were different. The adsorption energy, Mulliken charge population, electronic state density, and charge density difference of the three organic acids on the surfaces of α‐HH were calculated by well‐defined ab initio calculations. The results showed that the synergistic effect of ‐COOH groups is necessary for the effective crystallization of α‐HH. Organic acids interact with the Ca atoms on the crystal surface, as evidenced by their preferential adsorption on the top surface of α‐HH crystals (002). This interaction occurs through a double‐dentate chelation between the carboxyl oxygen atoms at both ends of the organic acid and the Ca atoms on the crystal surface, resulting in the formation of a six‐membered cyclic organic acid calcium complex. This complex hinders ion diffusion and the stacking of crystal surfaces, leading to a decrease in the growth rate along the c‐axis and promoting more extensive crystal development and larger crystal sizes. The work provides insight into the preparation of short prismatic α‐HH using organic acid crystallizing agents.

Exploration of the two-dimensional transition metal phosphide MoP2 as anode for Na/K ion batteries

Transition metal phosphides are regarded to be potential anode materials for alkali metal ion batteries with abundant availability of the constituent elements. However, the volume changes and resulting structure deterioration during the charge-discharge process are challenges. Using evolutionary search combined with ab initio calculations, we discover a dynamically, thermally, and mechanically stable MoP2 monolayer, which turns out to be an excellent anode material for Na-ion batteries providing a high specific capacity of 339 mA h g−1, low diffusion barrier of 0.12 eV, and low open-circuit voltage of 0.48 V. The volume expansion (125%) is found to be decisively smaller than in the case of black phosphorus (443%), for example.

Fluorine, nitrogen doping, and triaxial strain effects on the structural stability and hydrogen storage properties of lithium hydride LiH: DFT investigation

This research comprehensively addressed various aspects of hydrogen storage, with a focus on metallic hydride materials, lithium hydride LiH, one of the lightest reversible metal hydrides, boasts a remarkable gravimetric density of up to 12.67 wt% and an impressive volumetric capacity of 4.95 Kg/100 L. Despite these strengths, challenges accompany lithium hydride, such as its elevated formation energy and a high desorption temperature around 600 K–700 K. In this work, ab initio calculations based on Density Functional Theory (DFT) were used to study the thermodynamic and electronic properties of this material with the aim of reducing the high temperature of decomposition while preserving a significant gravimetric capacity and satisfactory stability in line with the U.S. Department of Energy (DOE) standards for solid-state hydrogen storage (ΔHf = - 40 kJ/mol.H2 and Td = 289 K–393 K). The results obtained show the influence of the doping effect firstly (Li1-xFxH, Li1-xNxH) on the improvement of the hydrogen storage properties, with a percentage gain of 50.64% for 4% doping with F and 49.08% for 8% doping with N. Secondly, a 38.63% gain in thermodynamic stability was observed by applying triaxial compressive stresses to the LiH compound.

Isomeric forms of 1,4-dioxane in a microsolvation environment

This study involves, for the first time, the comparative investigation of intermolecular interactions of the chair, 1,4 twist-boat, and 2,5 twist-boat conformations of 1,4-dioxane molecule within a microsolvation environment. In this context, the hydrogen bonding properties of binary, ternary and quaternary complexes involving the chair, 1,4 twist-boat, and 2,5 twist-boat conformations of the 1,4-dioxane molecule with water have been investigated by ab initio calculations. The ABCluster global search method in conjunction with the DFT level calculations has been utilized in this study to investigate the potential energy surfaces of 1,4-dioxane…(water)n (n = 0–3) clusters. The lowest relative energies of 1,4-dioxane-(water)n (n = 0–3) clusters are observed when the 1,4-dioxane molecule adopts the chair conformation, indicating its highest stability. However, it has been noted that structures in which the dioxane molecule is in the 2,5 twisted-boat conformation exhibit larger hydrogen bond energies. This observation suggests a notable impact of hydrogen bonding on the preferred molecular conformation. Furthermore, the relative energy differences between the conformers of 1,4-dioxane are influenced by the presence of water molecules in the system.

Radikalisierung von CO durch einkerniges Palladium(I)

AbstractEin einkerniges, T‐förmiges Palladium(I)‐d9‐ Metalloradikal (3), stabilisiert durch einen sterisch anspruchsvollen PNP‐Liganden mit Carbazolgerüst, wurde durch die Reduktion des Chloridokomplexes oder thermische Pd−C‐Bindungshomolyse des entsprechenden Neopentylkomplexes erhalten. Unter CO‐Druck bildete sich der Pd(I)‐Carbonylkomplex, der durch Röntgenbeugung strukturell charakterisiert wurde. Die Delokalisierung des ungepaarten Elektrons zum Carbonylkohlenstoff hin wurde durch EPR‐Spektroskopie nachgewiesen und durch DFT‐ und ab initio Methoden theoretisch modelliert. Das teilweise reduzierte und radikalisierte CO reagierte langsam mit Di(tert‐butyl)disulfid unter homolytischer S−S‐Spaltung und C−S‐Bindungsbildung zu dem entsprechenden Metallothioester.

Radicalizing CO by Mononuclear Palladium(I).

A mononuclear, T-shaped palladium(I) d9 metalloradical (3), stabilized by a bulky carbazole-based PNP-ligand, was obtained by reduction of palladium chloride or thermal Pd-C bond homolysis of the corresponding neopentyl complex. Pressurizing with CO gave the Pd(I) carbonyl complex, which was structurally characterized by X-ray diffraction. Delocalization of the unpaired electron to the carbonyl carbon was detected by EPR spectroscopy and theoretically modeled by DFT and ab initio methods. The partially reduced and radicalized CO slowly reacts with di(tert-butyl) disulfide under homolytic S-S cleavage and C-S bond formation to give the corresponding metallathioester.

Superalkalis with Hydrogen as Central Electronegative Atom and their Possible Applications: Ab Initio and DFT Study.

Superalkalis are unusual species having ionization energies lower than that of the alkali metals. These species with various applications are of great importance in chemistry due to their low ionization energies and strong reducing property. A typical superalkali contains a central electronegative core decorated with excess metal ligands. In the quest for novel superalkalis, we have designed the superalkalis HLi2, HLiNa and HNa2 using hydrogen as central electronegative atom for the first time employing high level ab initio (CCSD(T), MP2) and density functional theory (ωB97X-D) methods. The superalkalis exhibit very low ionization energies, even lower than that of cesium. Stability of these species is verified from binding energy and dissociation energy values. The superalkalis are capable of reducing SO2, NO, CO2, CO and N2 molecules by forming stable ionic complexes and therefore can be used as catalysts for the reduction or activation of systems possessing very low electron affinities. The superalkalis form stable supersalts with tailored properties when interact with a superhalogen. They also show remarkably high non-linear optical responses, hence could have industrial applications. It is hoped that this work will enrich the superalkali family and spur further theoretical and experimental research in this direction.

Derivation of Miller’s rule for the nonlinear optical susceptibility of a quantum anharmonic oscillator

Miller’s rule is an empirical relation between the nonlinear and linear optical coefficients that applies to a large class of materials but has only been rigorously derived for the classical Lorentz model with a weak anharmonic perturbation. In this work, we extend the proof and present a detailed derivation of Miller’s rule for an equivalent quantum-mechanical anharmonic oscillator. For this purpose, the classical concept of velocity-dependent damping inherent to the Lorentz model is replaced by an adiabatic switch-on of the external electric field, which allows a unified treatment of the classical and quantum-mechanical systems using identical potentials and fields. Although the dynamics of the resulting charge oscillations, and hence the induced polarizations, deviate due to the finite zero-point motion in the quantum-mechanical framework, we find that Miller’s rule is nevertheless identical in both cases up to terms of first order in the anharmonicity. With a view to practical applications, especially in the context of ab initio calculations for the optical response where adiabatically switched-on fields are widely assumed, we demonstrate that a correct treatment of finite broadening parameters is essential to avoid spurious errors that may falsely suggest a violation of Miller’s rule, and we illustrate this point by means of a numerical example.

Molecular insight into the initial hydration of tricalcium aluminate

Portland cement (PC) is ubiquitously used in construction for centuries, yet the elucidation of its early-age hydration remains a challenge. Understanding the initial hydration progress of tricalcium aluminate (C3A) at molecular scale is thus crucial for tackling this challenge as it exhibits a proclivity for early-stage hydration and plays a pivotal role in structural build-up of cement colloids. Herein, we implement a series of ab-initio calculations to probe the intricate molecular interactions of C3A during its initial hydration process. The C3A surface exhibits remarkable chemical activity in promoting water dissociation, which in turn facilitates the gradual desorption of Ca ions through a metal-proton exchange reaction. The dissolution pathways and free energies of these Ca ions follow the ligand-exchange mechanism with multiple sequential reactions to form the ultimate products where Ca ions adopt fivefold or sixfold coordination. Finally, these Ca complexes reprecipitate on the remaining Al-rich layer through the interface-coupled dissolution-reprecipitation mechanism, demonstrating dynamically stable inner-sphere adsorption states. The above results are helpful in unmasking the early-age hydration of PC and advancing the rational design of cement-based materials through the bottom-up approach.

Unlocking Ultrafast Spin Transfer in Single-Magnetic-Center-Decorated Triangulene Systems.

Triangulene, as a typical open-shell graphene fragment, has attracted widespread attention for nanospintronics, promising to serve as building blocks in spin-logic units. Here, using ab initio calculations, we systematically study the laser-induced ultrafast spin-dynamic processes on triangulene nanoflakes, decorated with a transition-metal atom. The results reveal a competition between the induced magnetic center and the carbon edge of the triangulene, resulting in the coexistence of dual spin-density-distribution patterns on such single-magnetic-center systems, thus opening up possibilities of complex spin-dynamic scenarios beyond the spin flip. Interestingly, no matter what direction the spin points to, it is possible to achieve reversible spin-transfer processes using the same laser pulse. Increasing the pool of elementary processes to contain not only spin-direction-dependent but also spin-direction-independent scenarios allows for more versatile spin-logic operations, including classical handling of information and quantum computing. In the present work, we suggest downscaling nanospintronic devices by integrating triangulene-based nanostructures.

Improved Tensor Current Limit from ^{8}B β Decay Including New Recoil-Order Calculations.

A precision measurement of the β^{+} decay of ^{8}B was performed using the Beta-decay Paul Trap to determine the β-ν angular correlation coefficient a_{βν}. The experimental results were combined with new abinitio symmetry-adapted no-core shell-model calculations to yield the second-most precise measurement from Gamow-Teller decays, a_{βν}=-0.3345±0.0019_{stat}±0.0021_{syst}. This value agrees with the standard model value of -1/3 and improves uncertainties in ^{8}B by nearly a factor of 2. By combining results from ^{8}B and ^{8}Li, a tight limit on tensor current coupling to right-handed neutrinos was obtained. A recent global evaluation of all other precision β decay studies suggested a nonzero value for right-handed neutrino coupling in contradiction with the standard model at just above 3σ. The present results are of comparable sensitivity and do not support this finding.

Collaboration on Machine-Learned Potentials with IPSuite: A Modular Framework for Learning-on-the-Fly.

The field of machine learning potentials has experienced a rapid surge in progress, thanks to advances in machine learning theory, algorithms, and hardware capabilities. While the underlying methods are continuously evolving, the infrastructure for their deployment has lagged. The community, due to these rapid developments, frequently finds itself split into groups built around different implementations of machine-learned potentials. In this work, we introduce IPSuite, a Python-driven software package designed to connect different methods and algorithms from the comprehensive field of machine-learned potentials into a single platform while also providing a collaborative infrastructure, helping ensure reproducibility. Furthermore, the data management infrastructure of the IPSuite code enables simple model sharing and deployment in simulations. Currently, IPSuite supports six state-of-the-art machine learning approaches for the fitting of interatomic potentials as well as a variety of methods for the selection of training data, running of ab initio calculations, learning-on-the-fly strategies, model evaluation, and simulation deployment.

The structure of appalachian coal: Experiments and Ab initio modeling

This study focuses on the construction of small-scale atomistic representations of three Appalachian coals of different ranks– high volatile bituminous, low volatile bituminous, and semi-anthracite. Ultimate, proximate, 13C NMR, FTIR, and XPS data were used to infer 2D and construct multiple 3D molecular models for each coal. A new simulation strategy for structure optimization, termed “Sectioned Optimization”, is introduced to ensure energetically stable configurations of the 3D coal models. Density functional methods are applied to the models, improving their quality, and giving insight into the limitations of empirical simulations in this complex system. The structural models were validated ex post facto using a density functional code, VASP. We describe the distribution of local atomic environments in the models to emphasize the significant structural distinctions between the three coal ranks. We also report the first ab initio vibrational density of states calculations for coal and compare it to FTIR and Inelastic Neutron Scattering experiments and identify vibrational modes using ab initio calculations. We also provide animations of the vibrational normal modes in coal that are consistent with FTIR band assignments. We show that the specific heat capacity compares favorably with experimental data.

Extending carbon chemistry at high-pressure by synthesis of CaC2 and Ca3C7 with deprotonated polyacene- and para-poly(indenoindene)-like nanoribbons

Metal carbides are known to contain small carbon units similar to those found in the molecules of methane, acetylene, and allene. However, for numerous binary systems ab initio calculations predict the formation of unusual metal carbides with exotic polycarbon units, [C6] rings, and graphitic carbon sheets at high pressure (HP). Here we report the synthesis and structural characterization of a HP-CaC2 polymorph and a Ca3C7 compound featuring deprotonated polyacene-like and para-poly(indenoindene)-like nanoribbons, respectively. We also demonstrate that carbides with infinite chains of fused [C6] rings can exist even at conditions of deep planetary interiors ( ~ 140 GPa and ~3300 K). Hydrolysis of high-pressure carbides may provide a possible abiotic route to polycyclic aromatic hydrocarbons in Universe.

Spontaneous Wetting Induced by Contact-Electrification at Liquid-Solid Interface.

Wettability significantly influences various surface interactions and applications at the liquid-solid interface. However, the understanding is complicated by the intricate charge exchange occurring through contact electrification (CE) during this process. The understanding of the influence of triboelectric charge on wettability remains challenging, especially due to the complexities involved in concurrently measuring contact angles and interfacial electrical signals. Here, the relationship is investigated between surface charge density and change of contact angle of dielectric films after contact with water droplets. It is observed that the charge exchange when water spared lead to a spontaneous wetting phenomenon, which is termed as the contact electrification induced wetting (CEW). Notably, these results demonstrate a linear dependence between the change of contact angle (CA) of the materials and the density of surface charge on the solid surface. Continuous CEW tests show that not only the static CA but also the dynamics of wetting are influenced by the accumulation charges at the interface. The mechanism behind CEW involves the redistribution of surface charges on a solid surface and polar water molecules within liquid. This interaction results in a decrease in interface energy, leading to a reduction in the CA. Ab initio calculations suggest that the reduction in interface energy may stem from the enhanced surface charge on the substrate, which strengthens the hydrogen bond interaction between water and the substrate. These findings have the potential to advance the understanding of CE and wetting phenomena, with applications in energy harvesting, catalysis, and droplet manipulation at liquid-solid interfaces.

Investigation of possible spin frustration in isolated isosceles MnIIINiII2 Triangle: Experimental and theoretical studies

Spin frustration is a unique phenomenon in magnetic complexes, where if a spin fails to lower the total energy of the system, by orienting itself in relative to its adjacent spins, it is termed as frustrated. In this work, we discuss about the magnetic properties, and the possibility of spin frustration in our isolated [NiII2MnIII(hep)4(PhCO2)(N3)2] (Hhep = 2-(2-hydroxyethyl) pyridine) having an isosceles NiII2MnIII triangle. The triangular MnIIINiII2 core was held together by two μ3-alkoxide bridges. The magnetic properties of this complex were studied in detail. Variable temperature magnetic susceptibility data of the complex in the range of 1.8 to 300 K, indicates the presence of stronger intramolecular antiferromagnetic coupling between two NiII centres than between NiII and MnIII ions. Experimentally, the ground state of the complex was found to be a mixture of E(2,0) and E(1,1) states, suggesting our complex to be close to a spin frustrated system which was supported by ab initio calculations.

Exploring Challenging Properties of Liquid Metallic Systems through Machine Learning: Liquid La and Li4Pb Systems.

In this machine learning (ML) study, we delved into the unique properties of liquid lanthanum and the Li4Pb alloy, revealing some unexpected features and also firmly establishing some of the debated characteristics. Leveraging interatomic potentials derived from ab initio calculations, our investigation achieved a level of precision comparable to first-principles methods while at the same time entering the hydrodynamic regime. We compared the structure factors and pair distribution functions to experimental data and unearthed distinctive collective excitations with intriguing features. Liquid lanthanum unveiled two transverse collective excitation branches, each closely tied to specific peaks in the velocity autocorrelation function spectrum. Furthermore, the analysis of the generalized specific heat ratio in the hydrodynamic regime investigated with the ML molecular dynamics simulations uncovered a peculiar behavior, impossible to discern with only ab initio simulations. Liquid Li4Pb, on the other hand, challenged existing claims by showcasing a rich array of branches in its longitudinal dispersion relation, including a high-frequency LiLi mode with a nonhydrodynamic optical character that maintains a finite value as q → 0. Additionally, we conducted an in-depth analysis of various transport coefficients, expanding our understanding of these liquid metallic systems. In summary, our ML approach yielded precise results, offering new and captivating insights into the structural and dynamic aspects of these materials.

Photocleavage of Aliphatic C–C Bonds in the Interstellar Medium

Ultraviolet (UV) processing in the interstellar medium (ISM) induces the dehydrogenation of hydrocarbons. Aliphatics, including alkanes, are present in different interstellar environments, being prevalently formed in evolved stars; thus, the dehydrogenation by UV photoprocessing of alkanes plays an important role in the chemistry of the ISM, leading to the formation of unsaturated hydrocarbons and eventually to aromatics, the latter ubiquitously detected in the ISM. Here, through combined experimental results and ab initio calculations, we show that UV absorption (mainly at the Lyα emission line of hydrogen at 121.6 nm) promotes an alkane to an excited Rydberg state from where it evolves toward fragmentation, inducing the formation of olefinic C=C bonds, which are necessary precursors of aromatic hydrocarbons. We show that the photochemistry of aliphatics in the ISM does not primarily produce direct hydrogen elimination but preferential C–C photocleavage. Our results provide an efficient synthetic route for the formation of unsaturated aliphatics, including propene and dienes, and suggest that aromatics could be formed in dark clouds by a bottom-up mechanism involving molecular fragments produced by UV photoprocessing of aliphatics.

Synthesis, Spectral Characterization and Photoluminescence of 3-chloro-6-methoxy-2-(methylsulfanyl)quinoxaline in Different Solvents: An Experimental and Theoretical Investigation Using DFT.

In the present work, we synthesized 3-chloro-6-methoxy-2-(methyl sulfanyl) quinoxaline (3MSQ) using a microwave-assisted synthesis method. The physicochemical structural analysis of the synthesized compound utilizing 1H-NMR, 13C-NMR, and FT-IR spectroscopy techniques. The photophysical properties of 3MSQ was examined through absorption and fluorescence spectroscopy. Spectroscopic analyses revealed a bathochromic shift in both absorption and fluorescence spectra, attributed to the π → π* transition. Ground and excited state dipole moments was experimentally determined using the solvatochromic shift method, employing various correlations such as Lippert's, Bakhshiev's, Kawski-Chamma-Viallet's equations, and solvent polarity parameters. Our findings indicate that the excited state dipole moments exceed those of the ground state, suggesting increased polarity in the excited state. Further, the while detailed bond length, bond angles, dihedral angles, Mulliken charge distribution, ground state dipole moments and HOMO-LUMO energy gap estimated through ab initio computations using Gaussian-09W. The value of energy band gap obtained from both the methods are in good agreement. Furthermore, employing DFT computational analysis, we identified reactive centers such as electrophilic and nucleophilic sites using molecular electrostatic potential (MESP) 3D plots. Additionally, CIE chromaticity analysis was performed to understand the photoluminescent properties of 3MSQ. The insights derived from these analyses contribute to a better understanding of the molecule's electronic structure, photophysical properties, and solute-solvent interactions, thus providing valuable information regarding its behaviour and characteristics under diverse conditions. These results contribute to a comprehensive understanding of the molecular structure and properties of 3-chloro-6-methoxy-2-(methyl sulfanyl) quinoxaline (3MSQ).