Exploration of Free Energy Surface of the Au10 Nanocluster at Finite Temperature.

The first step in comprehending the properties of Au10 clusters is understanding the lowest energy structure at low and high temperatures. Functional materials operate at finite temperatures; however, energy computations employing density functional theory (DFT) methodology are typically carried out at zero temperature, leaving many properties unexplored. This study explored the potential and free energy surface of the neutral Au10 nanocluster at a finite temperature, employing a genetic algorithm coupled with DFT and nanothermodynamics. Furthermore, we computed the thermal population and infrared Boltzmann spectrum at a finite temperature and compared it with the validated experimental data. Moreover, we performed the chemical bonding analysis using the quantum theory of atoms in molecules (QTAIM) approach and the adaptive natural density partitioning method (AdNDP) to shed light on the bonding of Au atoms in the low-energy structures. In the calculations, we take into consideration the relativistic effects through the zero-order regular approximation (ZORA), the dispersion through Grimme's dispersion with Becke-Johnson damping (D3BJ), and we employed nanothermodynamics to consider temperature contributions. Small Au clusters prefer the planar shape, and the transition from 2D to 3D could take place at atomic clusters consisting of ten atoms, which could be affected by temperature, relativistic effects, and dispersion. We analyzed the energetic ordering of structures calculated using DFT with ZORA and single-point energy calculation employing the DLPNO-CCSD(T) methodology. Our findings indicate that the planar lowest energy structure computed with DFT is not the lowest energy structure computed at the DLPN0-CCSD(T) level of theory. The computed thermal population indicates that the 2D elongated hexagon configuration strongly dominates at a temperature range of 50-800 K. Based on the thermal population, at a temperature of 100 K, the computed IR Boltzmann spectrum agrees with the experimental IR spectrum. The chemical bonding analysis on the lowest energy structure indicates that the cluster bond is due only to the electrons of the 6 s orbital, and the Au d orbitals do not participate in the bonding of this system.

Deciphering Pyramidanes: A Quantum Chemical Topology Approach.

C[C4H4], the simplest compound of the [4]-pyramidane family, has so far eluded experimental characterization, although several of its analogs E[C4(SiMe3)4], in which the E apex atom is a tetrel group element, have been successfully prepared. The non-classical bonding mode of E, similar to that found in propellanes, has prompted a considerable number of theoretical studies to unravel the nature of the apex-base interaction. Here, we contribute to this knowledge by analyzing the electron localization function (ELF) and classical QTAIM descriptors; as well the statistical distribution of electrons in atomic regions by means of the so-called electron distribution functions (EDFs), calculation of multicenter indices (MCI) as aromaticity descriptors and by performing orbital invariant energy decompositions with the interacting quantum atoms (IQA) approach on a series of E[C4(SiMe3)4] compounds. We find that the bonding evolves from covalent to electrostatic as E changes from C to Pb, with an anomaly when E=Si, which is shown to be the most charged moiety, compatible with an aromatic [C4(SiMe3)4]2- scaffold in the pyramidane base.

Quantification of the Donor-Acceptor Character of Ligands by the Effective Fragment Orbitals.

Metal-ligand interactions are at the heart of transition metal complexes. The Dewar-Chat-Duncanson model is often invoked, whereby the metal-ligand bonding is decomposed into the simultaneous ligand→metal electron donation and the metal→ligand back-donation. The separate quantification of both effects is not a trivial task, neither from experimental nor computational exercises. In this work we present the effective fragment orbitals (EFOs) and their occupations as a general procedure beyond the Kohn-Sham density functional theory (KS-DFT) framework for the identification and quantification of donor-acceptor interactions, using solely the wavefunction of the complex. Using a common Fe(II) octahedral complex framework, we quantify the σ-donor, π-donor, and π-acceptor character for a large and chemically diverse set of ligands, by introducing the respective descriptors σd, πd, and πa. We also explore the effect of the metal size, coordination number, and spin state on the donor/acceptor features. The spin-state is shown to be the most critical effect, inducing a systematic decrease of the sigma donation and π-backdonation going from low spin to high spin. Finally, we illustrate the ability of the EFOs to rationalize the Tolman electronic parameter and the trans influence in planar square complexes in terms of these new descriptors.

Chemical bonding in phase-change chalcogenides.

Almost all phase-change memory materials (PCM) contain chalcogen atoms, and their chemical bonds have been denoted both as 'electron-deficient' [sometimes referred to as 'metavalent'] and 'electron-rich' ['hypervalent', multicentre]. The latter involve lone-pair electrons. We have performed calculations that can discriminate unambiguously between these two classes of bond and have shown that PCM have electron-rich, 3c-4e ('hypervalent') bonds. Plots of charge transferred between (ET) and shared with (ES) neighbouring atoms cannot on their own distinguish between 'metavalent' and 'hypervalent' bonds, both of which involve single-electron bonds. PCM do not exhibit 'metavalent' bonding and are not electron-deficient; the bonding is electron-rich of the 'hypervalent' or multicentre type.

Current opinion on the prospect of mapping electronic orbitals in the transmission electron microscope: State of the art, challenges and perspectives.

The concept of electronic orbitals has enabled the understanding of a wide range of physical and chemical properties of solids through the definition of, for example, chemical bonding between atoms. In the transmission electron microscope, which is one of the most used and powerful analytical tools for high-spatial-resolution analysis of solids, the accessible quantity is the local distribution of electronic states. However, the interpretation of electronic state maps at atomic resolution in terms of electronic orbitals is far from obvious, not always possible, and often remains a major hurdle preventing a better understanding of the properties of the system of interest. In this review, the current state of the art of the experimental aspects for electronic state mapping and its interpretation as electronic orbitals is presented, considering approaches that rely on elastic and inelastic scattering, in real and reciprocal spaces. This work goes beyond resolving spectral variations between adjacent atomic columns, as it aims at providing deeper information about, for example, the spatial or momentum distributions of the states involved. The advantages and disadvantages of existing experimental approaches are discussed, while the challenges to overcome and future perspectives are explored in an effort to establish the current state of knowledge in this field. The aims of this review are also to foster the interest of the scientific community and to trigger a global effort to further enhance the current analytical capabilities of transmission electron microscopy for chemical bonding and electronic structure analysis.

Glued-bamboo composite based on a highly cross-linked cellulose-based adhesive and an epoxy functionalized bamboo surface.

Bamboo, as a renewable bioresource, exhibits advantages of fast growth cycle and high strength. Bamboo-based composite materials are a promising alternative to load-bearing structural materials. It is urgent to develop high-performance glued-bamboo composite materials. This study focused on the chemical bonding interface to achieve high bonding strength and water resistance between bamboo and dialdehyde cellulose-polyamine (DAC-PA4N) adhesive by activating the bamboo surface. The bamboo surface was initially modified in a directional manner to create an epoxy-bamboo interface using GPTES. The epoxy groups on the interface were then chemically crosslinked with the amino groups of the DAC-PA4N adhesive, forming covalent bonds within the adhesive layer. The results demonstrated that the hot water strength of the modified bamboo was improved by 75.8 % (from 5.17 to 9.09 MPa), and the boiling water strength was enhanced by 232 % (from 2.10 to 6.99 MPa). The bonding and flexural properties of this work are comparable to those of commercial phenolic resin. The activation modification of the bamboo surface offers a novel approach to the development of low-carbon, environmentally friendly, and sustainable bamboo engineering composites.

Classical versus Collective Interactions in Asymmetric Trigonal Bipyramidal Alkaline Metal-Boron Halide Complexes.

Collective interactions are a novel type of chemical bond formed between metals and electron-rich substituents around an electron-poor central atom. So far only a limited number of candidates for having collective interactions are reported. In this work, we extend the newly introduced concept of collective bonding to a series of neutral boron complexes with the general formula M2BX3 (M=Li, Na, and K; X=F, Cl, and Br). Our state-of-the-art ab initio computations suggest that these complexes form trigonal bipyramidal structures with a D3h to C3v distortion along the C3 axis of symmetry. The BX3 unit in the complexes distorts from planar to pyramidal akin to a sp3 hybridized atom. Interestingly, the interaction of the metals with the pyramidal side of BX3, where the lone pair in a hypothetical [BX3]2- should be located, is weaker than the interactions of metals with the inverted side, i. e., the middle of three halogen atoms. The origin of this stronger interaction can be explained by the formation of collective interactions between metals and halogen atoms as we explored via energy decomposition within the context of the theory of interacting quantum atoms, IQA.

Chemical bonding dictates drastic critical temperature difference in two seemingly identical superconductors.

Though YB6 and LaB6 share the same crystal structure, atomic valence electron configuration, and phonon modes, they exhibit drastically different phonon-mediated superconductivity. YB6 superconducts below 8.4 K, giving it the second-highest critical temperature of known borides, second only to MgB2. LaB6 does not superconduct until near-absolute zero temperatures (below 0.45 K), however. Though previous studies have quantified the canonical superconductivity descriptors of YB6's greater Fermi-level (Ef) density of states and higher electron-phonon coupling (EPC), the root of this difference has not been assessed with full detail of the electronic structure. Through chemical bonding, we determine low-lying, unoccupied 4f atomic orbitals in lanthanum to be the key difference between these superconductors. These orbitals, which are not accessible in YB6, hybridize with π B-B bonds and bring this π-system lower in energy than the σ B-B bonds otherwise at Ef. This inversion of bands is crucial: the optical phonon modes we show responsible for superconductivity cause the σ-orbitals of YB6 to change drastically in overlap, but couple weakly to the π-orbitals of LaB6. These phonons in YB6 even access a crossing of electronic states, indicating strong EPC. No such crossing in LaB6 is observed. Finally, a supercell (the M k-point) is shown to undergo Peierls-like effects in YB6, introducing additional EPC from both softened acoustic phonons and the same electron-coupled optical modes as in the unit cell. Overall, we find that LaB6 and YB6 have fundamentally different mechanisms of superconductivity, despite their otherwise near-identity.

Probing the geometric and electronic structures of the transition metal oxides RhOn-1/0 (n = 1-4) clusters.

The photoelectron spectroscopies of RhOn- (n = 1-2) were obtained via using the photoelectron velocity-map imaging (PE-VMI) approach. The experimental values of the adiabatic detachment energy (ADE) and vertical detachment energy (VDE) for RhO- were reported to be 1.58 ± 0.02 eV. The experimental AED and VDE values of RhO2- were reported to be 2.70 ± 0.02 eV and 2.79 ± 0.02 eV, respectively. The vibrational frequencies of RhO- and RhO2- measured from photoelectron spectra (PES) were 817(76) cm-1 and 932(55) cm-1, respectively. Based on the density functional theory (DFT), the RhOn-1/0 (n = 1-4) clusters were investigated. The optimized configurations of corresponding ground states and low-lying clusters were discovered. Meanwhile, the simulated photoelectron spectroscopy (PES) of RhOn- (n = 1-4) and the theoretical ADE and VDE values of RhOn- (n = 1-4) clusters were unveiled to assist future experimental studies of Rhodium oxide clusters. Moreover, the associated molecular orbitals (MOs), natural population analysis (NPA) and bond order analysis have been utilized to investigate the chemical bonding in these groups.

Towards high performance wood composites through interface customization with cellulose-based adhesive.

How to efficiently produce high performance plywood is of particular interest, while its sensitivity to moisture is overcome. This paper presents a simple and scalable strategy for the preparation of high-performance plywood based on the chemical bonding theory; a wood interfacial functionalized platform (WIFP) based on (3-aminopropyl) triethoxysilane (APTES) was established. Interestingly, the APTES-enhanced dialdehyde cellulose-based adhesive (DAC-APTES) was able to effectively establish chemically active adhesive interfaces; the dry/wet shear strength of WIFP/DAC-APTES adhesive was 3.15/1.31 MPa, which was much higher than 0.7 MPa (GB/T 9846-2015). The prepared plywood showed excellent wood-polymer interface adhesion, which exceeded the force that the wood itself could withstand. In addition, the DAC-APTES adhesive exhibits moisture evaporation-induced curing behavior at room temperature and can easily support the weight of an adult weighing 65.7 Kg. This research provides a novel approach for functionalized interface design of wood products, an effective means to prepare high-performance plywood.

Biomass-Derived Carbon Quantum Dots Chemical Bonding with Sn-Doped Bi2O2CO3 Endowed Fast Carriers' Dynamics and Stabilized Oxygen Vacancies for Efficient Decontamination of Combined Pollutants.

Surface defects on photocatalysts could promote carrier separation and generate unsaturated sites for chemisorption and reactant activation. Nevertheless, the inactivation of oxygen vacancies (OVs) would deteriorate catalytic activity and limit the durability of defective materials. Herein, bagasse-derived carbon quantum dots (CQDs) are loaded on the Sn-doped Bi2O2CO3 (BOC) via hydrothermal procedure to create Bi─O─C chemical bonding at the interface, which not only provides efficient atomic-level interfacial electron channels for accelerating carriers transfer, but also enhances durability. The optimized Sn-BOC/CQDs-2 achieves the highest photocatalytic removal efficiencies for levofloxacin (LEV) (88.7%) and Cr (VI) (99.3%). The elimination efficiency for LEV and Cr (VI) from the Sn-BOC/CQDs-2 is maintained at 55.1% and 77.0% while the Sn-BOC is completely deactivated after four cycle tests. Furthermore, the key role of CQDs in stabilization of OVs is to replace OVs as the active center of H2O and O2 adsorption and activation, thereby preventing reactant molecules from occupying OVs. Based on theoretical calculations of the Fukui index and intermediates identification, three possible degradation pathways of LEV are inferred. This work provides new insight into improving the stability of defective photocatalysts.

Chemical bonding in Uranium-based materials: A local vibrational mode case study of Cs 2 UO 2 Cl 4 and UCl 4 crystals.

The Local Vibrational Mode Analysis, initially applied to diverse molecular systems, was extended to periodic systems in 2019. This work introduces an enhanced version of the LModeA software, specifically designed for the comprehensive analysis of two and three-dimensional periodic structures. Notably, a novel interface with the Crystal package was established, enabling a seamless transition from molecules to periodic systems using a unified methodology. Two distinct sets of uranium-based systems were investigated: (i) the evolution of the Uranyl ion (UO 2 2 + ) traced from its molecular configurations to the solid state, exemplified by Cs 2 UO 2 Cl 4 and (ii) Uranium tetrachloride (UCl 4 ) in both its molecular and crystalline forms. The primary focus was on exploring the impact of crystal packing on key properties, including IR and Raman spectra, structural parameters, and an in-depth assessment of bond strength utilizing local mode perspectives. This work not only demonstrates the adaptability and versatility of LModeA for periodic systems but also highlights its potential for gaining insights into complex materials and aiding in the design of new materials through fine-tuning.

Understanding the Chemical Bond in Semiconductor/MXene Composites: TiO2 Clusters Anchored on the Ti2C MXene Surface.

First-principles calculations on titania clusters (TiO2)n (n=5 and 10) supported on the pristine Ti2C (0001) surface were carried out to understand the properties of semiconductor/MXene composites with implications in (photo)-catalysis. The reported results reveal a high exothermic interaction accompanied by a substantial charge transfer with a concomitant, notorious, deformation of the titania nanoclusters. The analysis of the density of states analysis of the composite systems evidences a metallic character with titania related states crossing the Fermi level. The picture of the chemical bonds is completed by the analysis of X-Ray Photoelectron Spectra (XPS) features, evidencing clear shifts of the C(1s) and O(1s) related peaks relative to the isolated systems that have a quite complex origin. This detailed analysis provides insights to experimentalists interested in the design and synthesis of these systems with possible applications in catalysis.

Polar covalent apex-base bonding in borapyramidanes probed by solid-state NMR and DFT calculations.

Pyramidane molecules have attracted chemists for many decades due to their regular shape, high symmetry and their correspondence in the macroscopic world. Recently, experimental access to a number of examples has been reported, in particular the rarely reported square pyramidal bora[4]pyramidanes. To describe the bonding situation of the nonclassical structure of pyramidanes, we present solid-state Nuclear Magnetic Resonance (NMR) as a versatile tool for deciphering such bonding properties for three now accessible bora[4]pyramidane and dibora[5]pyramidane molecules. 11 B solid-state NMR spectra indicate that the apical boron nuclei in these compounds are strongly shielded (around -50 ppm vs. BF3 -Et2 O complex) and possess quadrupolar coupling constants of less than 0.9 MHz pointing to a rather high local symmetry. 13 C-11 B spin-spin coupling constants have been explored as a measure of the bond covalency in the borapyramidanes. While the carbon-boron bond to the -B(C6 F5 )2 substituents of the base serves as an example for a classical covalent 2-center-2-electron (2c-2e) sp2 -carbon-sp2 -boron σ-bond with 1 J(13 C-11 B) coupling constants in the order of 75 Hz, those of the boron(apical)-carbon(basal) bonds in the pyramid are too small to measure. These results suggest that these bonds have a strongly ionic character, which is also supported by quantum-chemical calculations.

Metavalent or Hypervalent Bonding: Is There a Chance for Reconciliation?

A family of solids including crystalline phase change materials such as GeTe and Sb2 Te3 , topological insulators like Bi2 Se3, and halide perovskites such as CsPbI3 possesses an unconventional property portfolio that seems incompatible with ionic, metallic, or covalent bonding. Instead, evidence is found for a bonding mechanism characterized by half-filled p-bands and a competition between electron localization and delocalization. Different bonding concepts have recently been suggested based on quantum chemical bonding descriptors which either define the bonds in these solids as electron-deficient (metavalent) or electron-rich (hypervalent). This disagreement raises concerns about the accuracy of quantum-chemical bonding descriptors is showed. Here independent of the approach chosen, electron-deficient bonds govern the materials mentioned above is showed. A detailed analysis of bonding in electron-rich XeF2 and electron-deficient GeTe shows that in both cases p-electrons govern bonding, while s-electrons only play a minor role. Yet, the properties of the electron-deficient crystals are very different from molecular crystals of electron-rich XeF2 or electron-deficient B2 H6 . The unique properties of phase change materials and related solids can be attributed to an extended system of half-filled bonds, providing further arguments as to why a distinct nomenclature such as metavalent bonding is adequate and appropriate for these solids.

Nanoconfinement boosts affinity of hydrated zirconium oxides to arsenate: Surface complexation modeling study.

Nanoscale hydrated zirconium oxide (HZO) holds great potential in groundwater purification due to its ability to form inner-sphere coordination with arsenate. Despite being frequently used, especially as encapsulations in host materials for practical application in water treatment, the adsorption mechanisms of solutes on HZO are not appropriately explored, in particular for arsenate adsorption. In this study, we investigated the Zr-As coordination configuration and identified the most credible Zr-As configuration using surface complexation modeling (SCM), XPS and FT-IR analysis. The corresponding intrinsic coordination constants (Kintr) values was calculated by SCM, and the nanoconfinement effects were distinguished by comparing bare HZO with the HZO nanoparticles (NPs) encapsulated inside the strongly basic anion exchanger D201. Potentiometric titration suggests that the surface Zirconium hydroxyl groups (≡ZrOH) mainly exist in protonated form (≡ZrOH2+). Batch adsorption experiments demonstrate that the D201 hosts could adsorb As(V) through ion exchange by the quaternary ammonium groups under the low ionic strength (≤0.01 M NaNO3) and at pH > 6. The nanocomposite (HZO@D201) exhibits a higher adsorption capacity in a wide range of pH (3-10) and ionic strength (0.001-0.1 M NaNO3) than bare HZO. SCM simulations reveal that the coordination configuration of diprotonated monodentate mononuclear (MM-H2) dominates at pH 3-6, while deprotonated bidentate binuclear (BB-H0) dominates at pH > 7. For each configuration, the intrinsic coordination constants (Kintr) of HZO@D201 (10-0.66 and 10-16.10, respectively) are significantly higher than those of bare HZO (10-12.24 and 10-44.42, respectively), indicating a superior chemical bonding affinity caused by nanoconfinement. The obtained Kintr values are used to predict arsenate adsorption isotherms in pH 3 and 9, and the results align with the SCM simulation outcomes. This study may offer a feasible method for investigating the nanoconfinement effect of emerging nanocomposite adsorbents from a thermodynamic perspective, and provide reference coordination equilibrium constants of HZO for research and practical application.

Electronic structure of Li1,2,3 +,0,- and nature of the bonding in Li2,3 +,0,.

The current study of the small lithium molecules Li2 +,0,- and Li3 +,0,- focuses on the nature of the bonding in these molecules as well as their structures and energetics (bond energies, ionization energies, and electron affinities). Valence CASSCF (2s,2p) calculations incorporate nondynamical electron correlation in the calculations, while the corresponding multireference configuration interaction and coupled cluster calculations incorporate dynamical electron correlation. Treatment of nondynamical correlation is critical for properly describing the Li2,3 +,0,- molecules as well as the Li- anion with dynamical correlation, in general, only fine-tuning the predictions. All lithium molecules and ions are bound, with the Li3 + and Li2 + ions being the most strongly bound, followed by Li3 - , Li2 , Li2 - and Li3 . The minimum energy structures of Li3 +,0,- are, respectively, an equilateral triangle, an isosceles triangle, and a linear structure. The results of SCGVB calculations are analyzed to obtain insights into the nature of the bonding in these molecules. An important finding of this work is that interstitial orbitals, a concept first put forward by McAdon and Goddard in 1985, play an essential role in the bonding of all lithium molecules considered here except for Li2 . The interstitial orbitals found in the Li3 +,0 molecules likely give rise to the non-nuclear attractors/maxima observed in these molecules.

Decoding energy decomposition analysis: Machine-learned Insights on the impact of the density functional on the bonding analysis.

The concept of chemical bonding is a crucial aspect of chemistry that aids in understanding the complexity and reactivity of molecules and materials. However, the interpretation of chemical bonds can be hindered by the choice of the theoretical approach and the specific method utilized. This study aims to investigate the effect of choosing different density functionals on the interpretation of bonding achieved through energy decomposition analysis (EDA). To achieve this goal, a data set was created, representing four bonding groups and various combinations of functionals and dispersion correction schemes. The calculations showed significant variation among the different functionals for the EDA terms, with the dispersion correction terms exhibiting the highest variability. More information was extracted by using machine learning in combination with dimensionality reduction on the data set. Results indicate that, despite the differences in the EDA terms obtained from different functionals, the functional has the least significant impact, suggesting minimal influence on the bonding interpretation.

More Electropositive is More Electronegative: Atom Size Determines C=X Group Electronegativity.

Opposite to what one might expect, we find that the C=X group can become effectively more, not less, electronegative when the Pauling electronegativity of atom X decreases down Groups 16, 15, and 14 of the Periodic Table. Our quantum-chemical analyses, show that, and why, this phenomenon is a direct consequence of the increasing size of atom X down a group. These findings can be applied to tuning and improving the hydrogen-bond donor strength of amides H2 NC(=X)R by increasingly withdrawing density from the NH2 group. A striking example is that H2 NC(=SiR2 )R is a stronger hydrogen-bond donor than H2 NC(=CR2 )R.

Molecules Are Not Enough! Overcoming Students' Overgeneralization Tendencies by Comparing and Contrasting.

Many students assume a molecular structure for all substances, even after being instructed on the topic. But why do students struggle to understand key concepts like chemical bonding? One of the reasons is students' tendency to overgeneralize: Students wrongfully transfer characteristics from familiar (e.g., molecular substances) to lesser-known concepts (e.g., ionic compounds). In this article, possible reasons behind this commonly observed tendency are discussed and a possible didactical solution is proposed. Comparing and contrasting approaches increased students' ability to distinguish between similar concepts in mathematics.[1] The method of comparing and contrasting is therefore applied by simultaneously introducing the three types of chemical bonding to effectively tackle students' overgeneralization tendencies.