Weak Covalent Bonds Research Articles

AsS layered-structure compound: new kind of covalent crystals

The molecular phase As4S4 transforms under high pressures (>4 GPa) and temperatures (>400 °C) into a new covalent modification with a layered structure. This modification is metastable at normal pressure up to 260 °C and represents a chemically stable narrow gap (∼0.8 eV) semiconductor. The AsS high pressure phase has an orthorhombic structure (Pbc21 space group, a = 7.4537(7) A, b = 10.270(2) A, c = 18.258(1) A) with 32 As and 32 S atoms per elementary cell. The cost for the formation of a layered covalent structure at a non-stoichiometric composition is the presence in the structure of covalent bonds between the same type of atoms (As–As) and of anomalously weak covalent bonds between dissimilar atoms (As–S) with lengths 2.35–2.5 A atypically long for these bonds. One can expect that many of the known pseudo-molecular compounds, for example, As4S3, As4Se4, P4Se4 and others, under high pressure should transform to new covalent layered-structure semiconducting modifications as well.

The third-order optical nonlinearities of Ge–Ga–Sb(In)–S chalcogenide glasses

The third-order optical nonlinearities of 80GeS 2·(20 − x)Ga 2S 3· xY 2S 3 ( x = 0, 5, 10, 15, 20 and Y = Sb or In) chalcogenide glasses were investigated utilizing the Z-scan method at the wavelength of 800 nm and their linear optical properties and structure were also studied. By analyzing the compositional dependences and possible influencing factors including the linear refractive index, the concentration of lone electron pairs, the optical bandgap and the amount of weak covalent/homopolar bonds, it indicates that the electronic contribution in weak heteropolar covalent and homopolar metallic bonds is responsible for large nonlinear refractive index n 2 in the chalcogenide glasses. These chalcogenide glasses have characteristics of environmentally friendship, wide transparency in the visible region, high nonlinear refractive index n 2 and low nonlinear absorption coefficient β, and would be expected to be used in the all-optical switches working at 1330 nm and 1550 nm telecommunication wavelengths.

Third-order nonlinear optical properties of GeS_2-Sb_2S_3-CdS chalcogenide glasses

The third-order nonlinear optical properties of GeS(2)-Sb(2)S(3)-CdS chalcogenide glasses were investigated utilizing the Z-scan and femtosecond time-resolved optical Kerr effect (OKE) methods at the wavelength of 800 nm, respectively. The compositional dependences were analyzed and the influencing factors including the linear refractive index, the concentration of lone electron pairs, the optical bandgap and the amount of weak covalent/ homopolar bonds were discussed. A glass, i.e. 76GeS(2)·19Sb(2)S()·5CdS, with large nonlinear refrative index (n(2) = 5.63 × 10(-14) cm(2)/W), low nonlinear absorption coefficient (β = 0.88 cm/GW) and minimum figure of merit (FOM = 2βλ/n(2) = 2.51) was finally prepared. The electronic contribution in weak heterpolar covalent and homopolar bonds are responsible for large n(2) in chalcogenide glass, and the Sheik-Bahae rule combining the Moss rule are proved to be an effective guidance for estimating the third-order nonlinearities and further optimizing the compositions in chalcogenide glasses.

Evidence for Ligand Non-innocence in a Formally Ruthenium(I) Hydride Complex

Formally zerovalent, dinitrogen-bridged ruthenium complex, {[N(3)(Xyl)]Ru}(2)(mu-eta(1):eta(1)-N(2)) (1), where [N(3)(Xyl)] = 2,6-(XylN horizontal lineCMe)(2)C(5)H(3)N, reacts with excess H(2) to give the binuclear hydride species, {[N(3)]Ru(H)}(2)(mu-eta(1):eta(1)-N(2)) (2) bearing a single hydrogen per ruthenium. Complex 2 is an unusual example of a structurally characterized paramagnetic transition metal hydride, and the first such example for ruthenium. Structural data and DFT calculations suggest unpaired electron density is strongly delocalized onto the non-innocent [N(3)] ligand, with a relatively small degree of the metalloradical character implied by the Ru(I) formal oxidation state, and that the [N(3)](-)/Ru(II) formalism may be more informative. Consistent with an effective oxidation state greater than Ru(I), further reaction of 2 with excess H(2) to give metal dihydride species ([N(3)]RuH(2)(L)) is not observed. The magnetic moment of 2 (3.50 mu(B)) in solution is consistent with one unpaired electron per [N(3)]Ru moiety; however, 2 is diamagnetic in the solid due to close (3.26 A) head-to-tail contact between Ru pyridine planes of neighboring molecules. Although the geometry is reminiscent of the weak "pi-stacking" observed for closed-shell aromatic ring systems, DFT calculations indicate the structure and associated spin pairing result from in-phase overlap of the delocalized SOMOs on neighboring molecules-that is the interaction is best viewed as a weak covalent bond delocalized over 22 atoms.

The weak covalent bond in NgAuF (Ng=Ar, Kr, Xe): A challenge for subsystem density functional theory

We have assessed the accuracy of a representative set of currently available approximate kinetic-energy functionals used within the frozen-density embedding scheme for the NgAuF (Ng=Ar, Kr, Xe) molecules, which we partitioned into a Ng and a AuF subsystem. Although it is weak, there is a covalent interaction between these subsystems which represents a challenge for this subsystem density functional theory approach. We analyzed the effective-embedding potentials and resulting electron density distributions and provide a quantitative analysis of the latter from dipole moment differences and root-mean-square errors in the density with respect to the supermolecular Kohn-Sham density functional theory reference calculation. Our results lead to the conclusion that none of the tested approximate kinetic-energy functionals performs well enough to describe the bond between the noble gas and gold adequately. This observation contributes to the growing evidence that the current procedure to obtain approximate kinetic-energy functionals by reparametrizing functionals obtained via the "conjointness" hypothesis of Lee, Lee, and Parr [Phys. Rev. A 44, 768 (1991)] is insufficient to treat metal-ligand interactions with covalent character.

Monodentate Coordination of 4,4′‐Bipyridine Leading to a Supramolecular Network – Synthesis and Crystal Structure of [H2bpp][{Cu(Hbpy)2}{α‐HP2W18O62}]·4H2O

AbstractThe new supramolecular compound [H2bpp][{Cu(Hbpy)2}{α‐HP2W18O62}]·4H2O (1) (bpy = 4,4′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane) was synthesized hydrothermally and characterized byelemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray diffraction. In compound 1, the cationic fragment [Cu(Hbpy)2]+ connects to the Dawson anion through a coordinating Cu←O bond, and the copper atom is coordinated by another polyoxoanion through a weak covalent bond with a Cu1–O26 distance of 2.879(2) Å, forming a polymeric chain. The bpy ligand in [Cu(Hbpy)2]+ adopts a monodentate coordination mode, the other nitrogen atom of the bpy ligand is protonated. The protonated Hbpy+ acts as hydrogen‐bond donor and constructs a two‐dimensional double‐sheet supramolecular network involving the one‐dimensional chains through the hydrogen bonds. The H2bpp2+ ion connects twoα‐HP2W18O626– clusters from two supramolecular networks through hydrogen bonds and creates a three‐dimensional supramolecular architecture. The thermal decomposition of 1 happens over a wide temperature range (450–800 °C), which indicates that it might include complicated oxidation–reduction processes.

First-principles investigation of the electronic properties of multiferroic BaCoF4

The electronic properties of multiferroic BaCoF4 with ferroelectric antiferromagnetic phase and paraelectric phase are calculated using density functional theory with spin-polarized generalized-gradient approximation and plane wave pseudopotentials. It is found that anti-ferromagneticism probably favors to the ferroelectric stability at low temperature and the ion bond interaction is the main interation in the BaCoF4 system due to the strong electronegativity of F atoms. As to the CoF6 octahedron, there is entirely ionic bond between Co ion and F（2） or F（3） ions （bc plane）, but weak covalent bond between Co ion and F（1） ion and still weaker for F（4） ion. The ferroelectric distortion is only induced by relative displacement of Ba ion and F ion along c axis, and F（4） displacement contributes least to ferroelectric phase transformation . In addition, the energy of s and p orbitals of F（2） or F（3） ion is lower in the ferroelectric phase than in the centor-symmetric phase and the covalence character of F（1） ion, whose contribution to the displacement is the largest, is almost lost, which stabilizes the structure of the ferroelectric system.

Mechanochemistry: the varied applications of mechanical bond-breaking

Mechanochemistry means mechanical breakage of intramolecular bonds by external force and must be differentiated from molecular solid-state chemistry, where contacts between micronized molecular solids are created by the mechanical action for mutual approach of the reacting centers. After an outline of the mechanistic differences, the varied mechanochemistry is discussed. Grinding, milling, shearing, scratching, polishing, and rapid friction (for polymers also cutting, kneading, extruding) provide the mechanical impact for mechanochemistry, while sonication and shock waving for intramolecular bond breaking are generally described as thermal processes. The various types of mechanophysics (e.g., mechanoelectricity, conformational changes, thixotropy, rheopexy, stirring of Newtonian liquids or suspensions, etc.) are not treated here. Mechanochemistry covers solid-state reactions of infinitely covalent crystals, brittle metals, polymers, molecular solids with weak covalent bonds, strong intramolecular bond breakage in shearing Bridgman's anvil or by friction at lubrication of rapidly moving cold contacting surfaces, and single bond breaking or cutting. The diverse wealth of practical applications of mechanochemistry is outlined with typical examples for ceramics, mechanical alloying, hydrogen storage, organic syntheses, waste remediation, leachings, surface plasmas, radical formation, explosives, nanotube formation, nanoparticles grafting, polymer technology, radical initiation, scratch-less polishing, wear protection, lubrication, mechanochromism, nano-dissection, and many more.

X-ray and quantum-topological studies of intermolecular interactions in partially fluorinated quinoline crystals

An X-ray study of the crystals of bicyclic compounds containing fluorinated aromatic and nonfluorinated heteroaromatic rings, 5,6,7,8-tetrafluoroquinoline, 5,6,8-trifluoroquinoline, 5,7-difluoroquinoline, 5,7,8-trifluoro-2-phenylquinoline, and 5,7,8-trifluoro-6-trifluoromethylquinoline, was carried out. The basic supramolecular motifs and the underlying intermolecular interactions that control the lattice structure of these compounds were investigated. B3LYP DFT quantum-chemical calculations (6-311G(d,p) basis set) and the topological analysis of the electron density distribution in terms of Bader’s QTAIM theory were performed for the compounds. It is shown that the intermolecular interactions in question, traditionally regarded as nonvalent interactions, are related, to a definite extent, to the formation of very weak covalent chemical bonds in the intermolecular space due to the overlap of the “tails” of the molecular wave functions.

Bonding Study in All-Metal Clusters Containing Al4 Units

The nature of the bonding of a series of gas-phase all-metal clusters containing the Al4 unit attached to an alkaline, alkaline earth, or transition metal is investigated at the DFT level using Mulliken, quantum theory of atoms in molecules (QTAIM), and Hirshfeld iterative (Hirshfeld-I) atomic partitionings. The characterization of ionic, covalent, and metallic bonds is done by means of charge polarization and multicenter electron delocalization. This Article uses for the first time Hirshfeld-I multicenter indices as well as Hirshfeld-I based atomic energy calculations. The QTAIM charges are in line with the electronegativity scale, whereas Hirshfeld-I calculations display deviations for transition metal clusters. The Mulliken charges fail to represent the charge polarization in alkaline metal clusters. The large ionic character of Li-Al and Na-Al bonds results in weak covalent bonds. On the contrary, scarcely ionic bonds (Be-Al, Cu-Al and Zn-Al) display stronger covalent bonds. These findings are in line with the topology of the electron density. The metallic character of these clusters is reflected in large 3-, 4- and 5-center electron delocalization, which is found for all the molecular fragments using the three atomic definitions. The previously reported magnetic inactivity (based on means of magnetic ring currents) of the pi system in the Al42- cluster contrasts with its large pi electron delocalization. However, it is shown that the different results not necessary contradict each other.

EPR study on ligand-exchange reaction between bis(diethyldiselenocarbamato)copper(II) and some bis(acetylacetonato)copper(II) complexes

The paper is a study on the formation and properties of mixed-chelate copper(II) complexes, in which one ligand is strongly covalently bound diselenocarbamate (dsc), and the other belongs to a series of differently substituted acetylacetonates (acac), all forming weak covalent bonds. Thenoyltrifluoro- and trifluoro- substituted acetylacetonates only partly form mixed-chelate complexes, stable in toluene, benzene or dichloromethane, but gradually decomposing in chloroform or carbontetrachloride by analogy with Cu(Et 2dsc) 2 behavior in these solvents. Hexafluoro-acetylacetonato copper(II) completely turns into a mixed-chelate Cu(dsc)(hfacac), which remains unchanged for more than 8 months of monitoring in all solvents used. The stability of Cu(dsc)(hfacac) is attributed to the reduced remaining negative charge on selenium atom embarrassing the formation of weak D–A complex with haloalkanes. The obtained EPR parameters suggest significant lowering of the contribution of the 4s AO of copper(II) in the mixed-chelate complexes. It is shown that Cu(acac) 2 does not react with Cu(Et 2dsc) 2.

Metal ion complexes of thioformin: A density functional study

Some metal ion complexes of thioformin have been investigated by the density functional approach in order to understand its coordination chemistry. Due to the presence of the soft sulfur atom in addition to the oxide ion, thiohydroxamates exhibit a different coordination chemistry compared to their hydroxamate counterparts. It is found that the oxide ion forms bonds with metal ions that are predominantly ionic in nature while the sulfur atom is involved in weak covalent bond formation. Most of the complexes are found to be tetrahedrally distorted square planar structures, showing distinct cis and trans isomers. The exception is Zn(II), which forms tetrahedral complexes. The stabilities of the complexes have been linked with their antibiotic activity.

Study on the hydrothermal treatment of Shenhua coal

In this paper, the hydrothermal treatment of Shenhua coal was carried out under 0.1 MPa (initial pressure) nitrogen and different temperature. Effects of hydrothermal treatment on the structure and the hydro-liquefaction activity of Shenhua coal were investigated by the ultimate and proximate analyses, the FTIR measurements and TG analyses of hydrothermally treated coals, and the characterizations of extraction and swelling properties, and the batch hydro-liquefaction of treated coal were also carried out. The results indicate that hydrothermal treatment above 200 °C can increase the hydrogen content of treated coal and decrease the yield of volatiles and the content of ash, especially a large amount of CO and CH 4 are found in gas products obtained by the hydrothermal treatment above 250 °C. Hydrothermal treatment disrupts the weak covalent bond such as ether, ester and side-chain substituent by hydrolysis and pyrolysis, and changes the distribution of H-bond in coal. The swelling ratio and the Soxhlet extraction yield of treated coal decrease with the increase of hydrothermal treatment temperature. The conversion of liquefaction and the yield of CS 2/NMP mixed solvent extraction at ambient temperature are enhanced by hydrothermal treatment at 300 °C. Therefore hydrogen donation reactions and the rupture of non-covalent bond and weak covalent bonds present in the process of hydrothermal treatment resulting in the changes of structure and reactivity of Shenhua coal. The results show that the hydro-liquefaction activity of Shenhua coal can be improved by hydrothermal pretreatment between 250 °C and 300 °C.

Formation of titanium-carbide in a nanospace of C 78 fullerenes

Geometric and electronic structures of C 78 fullerenes encapsulating two Ti atoms and a C 2 molecule are studied by the first-principle total energy calculations. We find that the substantial hybridization between the 3d state of Ti atoms and the 2p state of C atoms results in the formation of weak covalent bonds between them and that the Ti atoms and the C 2 molecule form a zigzag chain inside the cage under the optimized geometry. Encapsulated C 2 molecule decreases the Coulomb repulsion energy between positively charged Ti atoms and rotates inside the cage. A plausible candidate for the structure of Ti 2C 2@C 78 extracted in a recent experiment is assigned by the density of states for the occupied electronic states.

Geometry, electronic properties, and thermodynamics of pure and Al-doped Li clusters

The first--principles density functional molecular dynamics simulations have been carried out to investigate the geometric, the electronic, and the finite temperature properties of pure Li clusters (Li$_{10}$, Li$_{12}$) and Al--doped Li clusters (Li$_{10}$Al, Li$_{10}$Al$_2$). We find that addition of two Al impurities in Li$_{10}$ results in a substantial structural change, while the addition of one Al impurity causes a rearrangement of atoms. Introduction of Al--impurities in Li$_{10}$ establishes a polar bond between Li and nearby Al atom(s), leading to a multicentered bonding, which weakens the Li--Li metallic bonds in the system. These weakened Li--Li bonds lead to a premelting feature to occur at lower temperatures in Al--doped clusters. In Li$_{10}$Al$_2$, Al atoms also form a weak covalent bond, resulting into their dimer like behavior. This causes Al atoms not to `melt' till 800 K, in contrast to the Li atoms which show a complete diffusive behavior above 400 K. Thus, although one Al impurity in Li$_{10}$ cluster does not change its melting characteristics significantly, two impurities results in `surface melting' of Li atoms whose motions are confined around Al dimer.

Probing the nature of hydrogen bonds in DNA base pairs

Energy decomposition analyses based on the block-localized wave-function (BLW-ED) method are conducted to explore the nature of the hydrogen bonds in DNA base pairs in terms of deformation, Heitler-London, polarization, electron-transfer and dispersion-energy terms, where the Heitler-London energy term is composed of electrostatic and Pauli-exchange interactions. A modest electron-transfer effect is found in the Watson-Crick adenine-thymine (AT), guanine-cytosine (GC) and Hoogsteen adenine-thymine (H-AT) pairs, confirming the weak covalence in the hydrogen bonds. The electrostatic attraction and polarization effects account for most of the binding energies, particularly in the GC pair. Both theoretical and experimental data show that the GC pair has a binding energy (-25.4 kcal mol(-1) at the MP2/6-31G** level) twice that of the AT (-12.4 kcal mol(-1)) and H-AT (-12.8 kcal mol(-1)) pairs, compared with three conventional N-H...O(N) hydrogen bonds in the GC pair and two in the AT or H-AT pair. Although the remarkably strong binding between the guanine and cytosine bases benefits from the opposite orientations of the dipole moments in these two bases assisted by the pi-electron delocalization from the amine groups to the carbonyl groups, model calculations demonstrate that pi-resonance has very limited influence on the covalence of the hydrogen bonds. Thus, the often adopted terminology "resonance-assisted hydrogen bonding (RHAB)" may be replaced with "resonance-assisted binding" which highlights the electrostatic rather than electron-transfer nature of the enhanced stabilization, as hydrogen bonds are usually regarded as weak covalent bonds.

First-Principles Description of Correlation Effects in Layered Materials

We present a first-principles description of anisotropic materials characterized by having both weak (dispersionlike) and strong covalent bonds, based on the adiabatic-connection fluctuation-dissipation theorem with density functional theory. For hexagonal boron nitride the in-plane and out-of-plane bonding as well as vibrational dynamics are well described both at equilibrium and when the layers are pulled apart. Bonding in covalent and ionic solids is also described. The formalism allows us to ping down the deficiencies of common exchange-correlation functionals and provides insight toward the inclusion of dispersion interactions into the correlation functional.

Electronic structure investigation ofTi3AlC2,Ti3SiC2, andTi3GeC2by soft x-ray emission spectroscopy

The electronic structures of epitaxially grown films of Ti3AlC2, Ti3SiC2 and Ti3GeC2 have been investigated by bulk-sensitive soft X-ray emission spectroscopy. The measured high-resolution Ti L, C K, Al L, Si L and Ge M emission spectra are compared with ab initio density-functional theory including core-to-valence dipole matrix elements. A qualitative agreement between experiment and theory is obtained. A weak covalent Ti-Al bond is manifested by a pronounced shoulder in the Ti L-emission of Ti3AlC2. As Al is replaced with Si or Ge, the shoulder disappears. For the buried Al and Si-layers, strongly hybridized spectral shapes are detected in Ti3AlC2 and Ti3SiC2, respectively. As a result of relaxation of the crystal structure and the increased charge-transfer from Ti to C, the Ti-C bonding is strengthened. The differences between the electronic structures are discussed in relation to the bonding in the nanolaminates and the corresponding change of materials properties.

Consecutive Ion Activation for Top Down Mass Spectrometry: Improved Protein Sequencing by Nozzle−Skimmer Dissociation

Mass spectra produced by nozzle-skimmer dissociation (NSD) have been little used in the past for structural characterization. NSD cannot be used on mass-separated ions (MS/MS), and for electrosprayed protein ions, previous NSD spectra showed backbone cleavages similar to those from energetic methods such as collisionally activated dissociation (CAD) or infrared multiphoton dissociation (IRMPD). However, our experimental configuration with Fourier transform (FT) MS makes possible three consecutive steps of NSD ion activation: thermal in the entrance capillary and collisional in both the nozzle-skimmer (N-S) region and the region after the skimmer before the quadrupole entrance lens (S-Q). In the high-pressure N-S region of adjustable path length, ions undergo high-frequency, low-energy collisions to rupture weak noncovalent or covalent bonds, with these "denatured" products then subjected to high-energy collisions in the low-pressure S-Q region to cleave strong backbone bonds. These NSD spectra, plus those from variable capillary thermal activation, of 8+ to 11+ ubiquitin ions electrosprayed from denatured solution show backbone cleavages between 74 of 75 amino acid pairs, vs 66 for CAD and 50 for IRMPD in the FTMS cell. Thermal activation by the inlet capillary of the newly desolvated 6+, 7+ ubiquitin ions from electrospraying the native conformer increases the NSD yield from 8% at 56 degrees C to 96% at 76 degrees C, but with little change in product branching ratios; this capillary heating has no effect on CAD or IRMPD of these ions collected in the FTMS cell. Ion desolvation with its concomitant H-bond strengthening appears to produce a transiently stable conformer whose formation can be prevented by capillary heating. The far more complex and stable noncovalent tertiary structures of large protein ions in the gas phase have made MS/MS difficult; initial inhibition of tertiary structure formation with immediate NSD ("prefolding dissociation") appears promising for the top down characterization of a 200-kDa protein.

An ELF and AIM study of NO 2 and N 2O 4

The B3LYP/cc-pvtz approach is used to obtain Kohn–Sham wavefunctions for NO 2 and N 2O 4 and several related compounds. ELF and AIM analyses on these systems lead to a better understanding of the unusual character of the NN bond in N 2O 4 in which competing Lewis structures with one or two electrons on the nitrogen atom in NO 2 lead to a very weak sigma covalent bond that receives essentially no bonding contribution from the pπ part of the molecule.