Bond Polarizability Research Articles

Commentary on the Models of Electronegativity

The concept of electronegativity is one of the most relevant concepts in the chemical sciences from the second half of the past century. It is used to understand the polarity of bonds, bond dipole ...

Density functional theory calculations and Hirshfeld surface analysis of propyl-para-hydroxybenzoate (PHB) for optoelectronic application

Abstract The geometries, electrostatic potential, Mulliken charge analysis, Natural Bond Orbital analysis and polarizabilities of propyl-para-hydroxybenzoate were calculated using B3LYP functional with 6-311++G(d,p) basis set. The calculated geometries are well matched with the experimental values. The Mullliken atomic charge analysis shows that the eventual charges are contained in the molecule. The NBO analysis explains the intramolecular charge transfer in the PHB molecule. The bonding features of the molecule were analyzed with the aid of Hirshfeld surface analysis. The frontier molecular orbital analysis showed the charge transfer obtained within the molecule. The calculated hyperpolarizability of the PHB molecule was 6.977E −30 esu and it was 8.9 times that of standard urea molecule.

Encapsulation effect of π-conjugated quaterthiophene on the radial breathing and tangential modes of semiconducting and metallic single-walled carbon nanotubes.

We developed a hybrid approach, combining the density functional theory, molecular mechanics, bond polarizability model and the spectral moment's method to compute the nonresonant Raman spectra of a single quaterthiophene (4T) molecule encapsulated into a single-walled carbon nanotube (metallic or semiconducting). We reported the optimal tube diameter allowing the 4T encapsulation. The influence of the encapsulation on the Raman modes of the 4T molecule and those of the nanotube (radial breathing modes and tangential modes) are analyzed. An eventual charge transfer between the 4T oligomer and the nanotube is discussed.

Effects of Solvent Polarity on Li-ion Diffusion in Polymer Electrolytes: An All-Atom Molecular Dynamics Study with Charge Scaling.

We herein report an all-atom molecular dynamics study on the role of solvent polarity for Li+ diffusion in polymer electrolytes using PEO–LiTFSI (poly(ethylene oxide)–lithium bis(trifluoromethane)sulfonimide) as a model system. By separating the effect of Tg and the effect of solvent polarity in our simulations, we show that the maximum in the diffusion coefficient of Li+ with respect to the dielectric constant of polymer solvent εp is due to transitions in the transport mechanism. In particular, it is found that the frequent interchain hopping involves the coordination of both PEO and TFSI. This optimal solvating ability of PEO at an intermediate value of εp leads to the fast ion conduction. These findings highlight the synergetic effect of solvent polarity and bond polarity on Li-ion diffusion in solid polymer electrolytes.

An Adduct of Sulfur Monoxide to a Frustrated Sn/P Lewis Pair.

The geminal frustrated Lewis pair (F5C2)3SnCH2P(tBu)2 (1) reacted with N‐sulfinylaniline PhNSO to afford the first sulfur monoxide adduct of a main group metal, (F5C2)3SnCH2P(tBu)2⋅SO (2), which contains a SnCPSO ring. The second product is a phenylnitrene adduct of 1. The surprising stability of 2 was compared with the stabilities of the so far inaccessible O2 and S2 adducts of 1. Attempts to prepare these from 1 and the elemental chalcogens (O2, S8, Se∞, Te∞) led to four‐membered SnCPE ring systems. Quantum‐chemical investigations of 2 demonstrate the bond polarity of the SO unit to stabilize 2.

Interception of the Bycroft-Gowland Intermediate in the Enzymatic Macrocyclization of Thiopeptides.

Thiopeptides are a broad class of macrocyclic, heavily modified peptide natural products that are unified by the presence of a substituted, nitrogen-containing heterocycle core. Early work indicated that this core might be fashioned from two dehydroalanines by an enzyme-catalyzed aza-[4 + 2] cycloaddition to give a cyclic-hemiaminal intermediate. This common intermediate could then follow a reductive path toward a dehydropiperidine, as in the thiopeptide thiostrepton, or an aromatization path to yield the pyridine groups observed in many other thiopeptides. Although several of the enzymes proposed to perform this cycloaddition have been reconstituted, only pyridine products have been isolated and any hemiaminal intermediates have yet to be observed. Here, we identify the conditions and substrates that decouple the cycloaddition from subsequent steps and allow interception and characterization of this long hypothesized intermediate. Transition state modeling indicates that the key amide-iminol tautomerization is the major hurdle in an otherwise energetically favorable cycloaddition. An anionic model suggests that deprotonation and polarization of this amide bond by TbtD removes this barrier and provides a sufficient driving force for facile (stepwise) cycloaddition. This work provides evidence for a mechanistic link between disparate cyclases in thiopeptide biosynthesis.

An Anomalous Magneto-Optic Effect in Epitaxial Indium Selenide Layers.

Single-phonon modes offer potential applications in quantum phonon optics, but the phonon density of states of most materials consist of mixed contributions from coupled phonons. Here, using theoretical calculations and magneto-Raman measurements, we report two single-phonon vibration modes originating from the breathing and opposite out-of-plane vibrations of InSe layers. These single-phonon vibrations exhibit an anticorrelated scattering rotations of the polarization axis under an applied vertical magnetic field; such an anomalous magneto-optical behavior is due to the reverse bond polarizations of two quantum atomic vibrations, which induce different symmetry for the corresponding Raman selection rules. A 180° (+90° and -90°) integrated scattering rotation angle of two single-phonon modes was achieved when the magnetic field was swept from 0 to 6 T. This work demonstrates new ways to manipulate the magneto-optic effect through phonon polarity-based symmetry control and opens avenues for exploring single-phonon-vibration-based nanomechanical oscillators and magneto-phonon-coupled physics.

DFT analysis of the interaction between Hg2+ and monodentate neutral ligands using NBO, EDA, and QTAIM.

We report thermodynamic, geometric, and electronic parameters for the interaction between neutral ligands and the [Hg(H2O)]2+ dication, using the B3LYP/6-311 + G(d,p) approach. Gibbs free energies for the interaction were employed to rank the affinity order of the several neutral ligands. To identify the parameters that characterize the affinity between the two fragments, the metal-ligand interaction was analyzed according to the EDA, NBO, and QTAIM decomposition schemes. The phosphine oxide showed the highest affinity for the Hg(H2O)2+ dication, mainly due to the P=O bond polarization. Ligands containing the sulfur atom, characterized by a high covalent component for the metal-ligand interaction, are the following in the interaction order. According to the Gibbs free energy for substitution of one water molecule in the [Hg(H2O)2]2+ complex, the sequence for the affinity order is: phosphine oxide > thioketone > thioesther > lactam > amide > amine > carboxylic acid > thiophene > ketone > esther > thiol > thiocyanate > ammonia > disulfide > aldehyde > ether > haloydrin > alcohol > enol > azide. Graphical abstract Synopsis The interaction between the Hg2+ cation and monodentate ligands containing S, O, or N atoms was evaluated in terms of energetic (bond strength, electrostatic and covalent interactions, donation energy), geometric (metal-ligand distance), electronic (atomic charges, orbital overlap, orbital hybridization) and topologic parameters.

Evaluation of Electronegativity Scales.

Scales of electronegativity values are used by chemists to describe numerous chemical features such as chemical mechanisms, bond polarity, band gap, atomic hardness, etc. While the many scales provide similar trends, all differ in their predictive quality. Confirmation of the quality of a new scale often uses a previous scale for comparison but does not use independent means to demonstrate the merits of the scale. Utilizing a table of binary compounds of known ionic, covalent, and metallic bonding characters, a means to evaluate electronegativity scales is developed here. By plotting the electronegativity values of the two bonded atoms in binary compounds of a known bonding character, a tripartite separation results that generally divides the three bond types. Using the results of graphs of this sort, the success of bonding separations of 14 different scales of electronegativity has been evaluated on the basis of three quantitative parameters that can provide a measure of the quality of the scales. Three scales, those of Allen, Martynov and Batsanov, and Nagle, have been shown to be superior in their ability to predict the expected separation of bond types. Since this scheme successfully demonstrates the ability to evaluate the quality of electronegativity scales, it can be applied to other scales to establish their effectiveness in predicting bond types in binary compounds and thus the quality of the scales. This scheme is applied to a recently published electronegativity scale to evaluate the ability to determine its quality.

Effect of Hydrogen Absorption on the Composition of the Amorphous Alloys Surface Layers

Hydrogen absorption leads to redistribution of the components of the surface layer of the amorphous alloy Fe73.8Si12.7B9.4Nb3.2Cu noncontact side, while the amorphous structure of this layer is preserved. The type of the micro-groups Fey Six changes in such a way that the ratio y: x decreases (to less than 1) and the chemical bond polarity decreases, as well. After degassing, the surface layer composition becomes similar to those before hydrogenation. The loss of the mechanical stability of the amorphous ribbon is accompanied by the formation of the micro-groups Fey Six with a decreased ratio of y: x.

Photoredox catalysis of As(III) by constructed [sbnd]C[dbnd]Sn[sbnd]S bonds: Using biomass as templates leads to bio‑carbon/SnS2 nanosheets capable of the efficient photocatalytic conversion of As(III) and calcium arsenate capture

In this paper, a new interface design strategy for bio‑carbon/SnS2 nanosheets equipped with CSnS bonds was proposed by using biomass as a template for the efficient photocatalytic conversion of As(III). The characterization results illustrated that the CSnS bonds could effectively prevent the agglomeration of SnS2, expand the photoresponse range and improve the hydrophilicity of the bio‑carbon/SnS2 composites while reducing their transfer resistance. Therefore, the construction of CSnS bonds could more efficiently promote the photoredox catalysis of As(III) to As(V) compared with pure SnS2, attributing to the polarization and conjugation effects of the CSn bonds. Meanwhile, CaSO4·nH2O (n = 0, 0.5, 2) could rapidly convert AsO43− into Ca3(AsO4)2 precipitates to eliminate arsenic from the aqueous solution in one step. In particular, 7500 μg/L As(III) could not only be photocatalyzed into As(V) but also be converted to Ca3(AsO4)2 to achieve the removal of arsenic within only 55 min in the coexistence of CaSO4. In addition, the electron transfer path in the photocatalytic oxidation system on arsenite was proposed according to the Mott-Schottky (MS) plots of SnS2 and graphitic carbon. The electron paramagnetic resonance (EPR) results implied that O2– and h+ were the main active substances in the photooxidation arsenic system and the effect of OH could be negligible. Thus, the possible mechanism of the photocatalytic conversion of As(III) was discussed.

Nonresonant Polarized Raman Spectra Calculations of Nitrogen-Doped Single-Walled Carbon Nanotubes: Diameter, Chirality, and Doping Concentration Effects.

Raman spectra of nitrogen-doped single-walled carbon nanotubes are calculated using the spectral moment's method combined with the bond polarizability model. The influence of the nanotube diameter and chirality is investigated. We also address the important question of the effect of the N-doping concentration, and we propose an equation to estimate the doping concentration from the knowledge of the tube diameter and the frequency of the radial breathing mode.

Water Promotion (or Inhibition) of Condensation Reactions Depends on Exposed Cerium Oxide Catalyst Facets

Nanoparticles with well-defined facets enable quantitative correlations between surface features and catalytic activity. Here, we explore the role of geometric and acid–base properties in the mechanism of aldol condensation catalyzed by ceria nanoshapes. In the crucial C–C coupling step, the two carbonyl adsorbates are bound to two adjacent cations. On the CeO2(110) plane, all atoms lie on the same layer, favoring the interaction between adsorbates and facilitating the bimolecular C–C coupling. Thus, the initial unimolecular deprotonation is rate-limiting. In contrast, the (100) and (111) planes have an open structure with O on the top layer and Ce on the layer below. The former O layer interferes between adsorbates linked to Ce sites, making the C–C coupling rate-limiting. Water helps in overcoming this spatial hindrance by remote bond polarization via H-bonds. Therefore, water promotion is only observed on those planes for which the bimolecular step is rate-limiting.

Exploring the Limits of Transition‐Metal Fluorination at High Pressures

AbstractFluorination is a proven method for challenging the limits of chemistry, both structurally and electronically. Here we explore computationally how pressures below 300 GPa affect the fluorination of several transition metals. A plethora of new structural phases are predicted along with the possibility for synthesizing four unobserved compounds: TcF7, CdF3, OsF8, and IrF8. The Ir and Os octaflourides are both predicted to be stable as quasi‐molecular phases with an unusual cubic ligand coordination, and both compounds formally correspond to a high oxidation state of +8. Electronic‐structure analysis reveals that otherwise unoccupied 6p levels are brought down in energy by the combined effects of pressure and a strong ligand field. The valence expansion of Os and Ir enables ligand‐to‐metal F 2p→M 6p charge transfer that strengthens M−F bonds and decreases the overall bond polarity. The lower stability of IrF8, and the instability of PtF8 and several other compounds below 300 GPa, is explained by the occupation of M−F antibonding orbitals in octafluorides with a metal‐valence‐electron count exceeding 8.

Exploring the Limits of Transition-Metal Fluorination at High Pressures.

Fluorination is a proven method for challenging the limits of chemistry, both structurally and electronically. Here we explore computationally how pressures below 300 GPa affect the fluorination of several transition metals. A plethora of new structural phases are predicted along with the possibility for synthesizing four unobserved compounds: TcF7 , CdF3 , OsF8 , and IrF8 . The Ir and Os octaflourides are both predicted to be stable as quasi-molecular phases with an unusual cubic ligand coordination, and both compounds formally correspond to a high oxidation state of +8. Electronic-structure analysis reveals that otherwise unoccupied 6p levels are brought down in energy by the combined effects of pressure and a strong ligand field. The valence expansion of Os and Ir enables ligand-to-metal F 2p→M 6p charge transfer that strengthens M-F bonds and decreases the overall bond polarity. The lower stability of IrF8 , and the instability of PtF8 and several other compounds below 300 GPa, is explained by the occupation of M-F antibonding orbitals in octafluorides with a metal-valence-electron count exceeding 8.

The effect of Tri- and Tetra-vacancies defects on the electronic and vibrational properties of (14, 5) chiral carbon nanotube

In this theoretical work, using the spectral moment’s method and the bond polarisability model, the non-resonant Raman spectra of (14,5) chiral carbon nanotube with Tri- and Tetra-vacancies defects were calculated. The evolution of the Raman lines of defectives CNTs as a function of the defects concentration was discussed. It is observed that, the Raman spectra of defective carbon nanotubes present the D-band around 1350 cm-1. The Raman characteristics modes of TriV and TetraV defects are identified. The evolution of the electronic density of states as a function of the defects concentration was investigated. This study can provide benchmark to understand the experimental data of defective CNTs.

Non resonant Raman spectra of homogeneous and inhomogeneous individual dimers of Single-walled Carbon Nanotubes (SWNTs)

We study the effects of the coupling between single-walled carbon nanotubes (SWNTs) on the phonons in homogeneous (identical nanotubes) and inhomogeneous (different nanotubes) dimers of SWNTs. Bond polarization theory and the spectral moments method (SMM) are used to calculate the non-resonant Raman frequencies of the breathing-like modes (BLMs) and tangential-like ones (TLMs). The dependence of the phonons on different structural parameters such as diameter and chirality is investigated. We focus on the dependence of the so-called Breathing-Like Modes (BLMs) of dimers originating from the van der Waals coupling of the Radial Breathing Modes (RBMs) of each individual tube forming the dimer. On the other hand, the TLM of dimer is reported and discussed. Distinct behaviors of the TLM are evidenced. The calculated of spectra are compared with the few experimental Raman data obtained on individual dimers.

Effect of SDBS solution on the surface potential properties of the Zhaozhuang coal

It is of great significance to study the effect of surfactants on the coal surface potential for effective dust suppression in mining faces. The effect of different concentrations of sodium dodecyl benzene sulfonate (SDBS) solution on the surface potential of the Zhaozhuang coal was measured by atomic force microscopy (AFM). The experimental results show that the SDBS solution has significant influence on the surface potential of the Zhaozhuang coal. The electrical characteristics of the coal surface at the nanometer scale are different from those of macroscopic or the mesoscopic level. The surface potential of coal is basically a normal distribution, showing certain electrical characteristics. The mean value of the surface potential of the Zhaozhuang coal is increased with the increase in concentration of the SDBS solution; when the concentration of the SDBS solution is 0.3%, the mean value of surface potential is 5.59 mv, which is about two times of the mean value of the surface potential without SDBS solution added. With the increase of the concentration of the SDBS solution, the maximum value of the surface potential of the Zhaozhuang coal increases, and the minimum value decreases. It shows that the SDBS solution has a significant effect on the potential distribution law and the magnitude of the coal surface. Subsequently, on the basis of the constructed Zhaozhuang coal macromolecule model, xtb and Multiwfn simulation software were used to calculate the molecular surface electrostatic potential value and electron density value of the Zhaozhuang coal molecules after adding water molecules. The variation law for the electrostatic potential surface of the molecule was obtained after adding numbers of water molecules to the surface of the coal molecule. The simulation results show that the area proportion of absolute molecular surface electrostatic potential greater than 10 kcal/mol is increased with the growth in the number of water molecules, while the area proportion of absolute molecular surface electrostatic potential less than 10 kcal/mol is decreased. Because of the free state O─H bond polarity of water molecules, the charges on the molecular surface are rearranged in order to change the electron density on the surface of coal molecules, which affects the overall electrostatic potential of the configuration.

Structurally Modulated Graphitic Carbon Nanofiber and Heteroatom (N,F) Engineering toward Metal-Free ORR Electrocatalysts for Polymer Electrolyte Membrane Fuel Cells

The present study, designates the heteroatoms (N,F) doped various graphitic carbon nanofibers (GNF) viz. GNF-linear segmented platelets, antlers, herringbone type and their structural deformations from pristine fiber with many open-edge active centers as metal-free, cost-effective electrocatalysts for ORR in polymer electrolyte membrane fuel cells. Heteroatoms introduction to GNF frameworks enlarge the lattice spacing between graphene platelets and brings the structural modulation. The developed GNF/N-F catalysts show excellent ORR activity with insensitive to CH3OH and demonstrated outstanding electrochemical potential cycling stability of 10,000 cycles with well-retained ORR kinetics without much loss in the activity. X-ray photoelectron spectroscopy investigation of GNF/N-F catalysts explicit the highly active forms of N (pyridinic, pyrrolic, graphitic-N) and semi-ionic, ionic C-F of F in the catalysts. The deep-rooted synergistic effect among N and F atoms induces to create more active-centres entrenched with extensive C-C bond polarization, larger charge delocalisation with larger spin density differences accomplished in GNF/N-F catalysts. Wide open-edge cavities, opened-tips and many extensively accessible facets collectively enhance the ORR activity of GNF-H/N-F catalyst. The present study unlocks a deep insight towards understanding of advanced metal-free electrocatalysts for efficient ORR in PEMFCs and metal-air batteries.

Enhanced Catalytic Performance of Subnano Copper Oxide Particles.

Subnanoparticles (SNPs) with ultrasmall particle sizes (<1 nm) have potential to provide catalytic activity that is superior to that of nanoparticles. Size-controlled CunOx (n = 12, 28, and 60) materials supported on zirconia, prepared using a dendritic macromolecular reactor, exhibited increased ionicity of the Cu-O bonds with a decrease in size of the particles, which was suggested on the basis of the peak intensity in the Cu 2p3/2 region. The polarization of the Cu-O bonds in the ultrasmall copper oxides provides size-dependent catalytic activity in aerobic oxidation of the CH3 group bonded with aromatic rings. The smallest Cu12Ox materials achieved an excellent large turnover number (TON = 40 206) without any significant deactivation.