A theoretical study of substitution effects on halogen–π interactions

Ab initio calculations are performed to analyse the existence of intermolecular halogen···π interactions in NCX complexes with YC≡CY, where X = Cl, Br and Y = H, CN, F, Cl, OH, NH₂, and CH₃. Molecular geometries and interaction energies of the complexes are investigated at the MP2/aug-cc-pVTZ level of theory. Our results indicate that the interaction energies for the NCX···YC≡CY complexes lie in the range between ?0.5 and ?5.9 kcal/mol. The physical nature of the interactions is studied using symmetry-adapted perturbation theory (SAPT). The stability of the X···π interactions is predicted to be attributable mainly to electrostatic and dispersion effects.     

The effect of hydrogen-bonding cooperativity on the strength and properties of σ-hole interactions: an ab initio study

Ab initio calculations at the MP2/aug-cc-pVTZ level of theory are performed to investigate the effect of hydrogen-bonding cooperativity on the strength and bonding properties of σ-hole interaction in linear FCl???(NCH)_n=2–5, FHS???(NCH)_n=2–5, FH₂P???(NCH)_n=2–5 and FH₃Si???(NCH)_n=2–5 clusters. It is found that the cooperative effects in the hydrogen-bonding tend to strengthen the σ-hole interaction. However, these effects are almost saturated in the larger clusters (n > 5). For a given cluster, the amount of bond contraction in FCl???(NCH)_n is more important than other systems. A nice linear relationship is found between the σ-hole bond energies and absolute ¹⁵N chemical shieldings or spin–spin coupling constants across the σ-hole bond.     

The strengthening effect of a hydrogen or lithium bond on the Z···N aerogen bond (Z = Ar,Kr and Xe): a comparative study

An ab initio study is performed on O₃Z···NCM···NCX (Z = Ar, Kr and Xe; M = H and Li; X = H, F and CH₃) complexes to investigate cooperativity effects between aerogen and hydrogen or lithium bonding interactions in these systems. To understand the cooperative effects, a detailed analysis of the binding distances, interaction energies and bonding properties is performed on these complexes. The results indicate that all Z···N and H/Li···N binding distances in the ternary complexes are shorter than those of corresponding binary systems. For a given M or X, cooperative energies increase as Z = Xe > Kr > Ar. Moreover, O₃Z···NCLi···NCX complexes exhibit a larger cooperative energy than O₃Z···NCH···NCX ones. The non-covalent interaction (NCI) index analysis indicates that the formation of an H/Li···N interaction in the ternary complexes shifts the location of the spike associated with the Z···N interaction towards the negative λ₂ρ values. This indicates that NCI analysis can be regarded as a useful tool for the study of cooperative effects between two different non-covalent interactions. Also, cooperative effects in O₃Z···NCM···NCX complexes make a decrease in ¹⁴N nuclear quadrupole coupling constants of NCH or NCLi molecule.     

Mutual influence between triel bond and cation–π interactions: an ab initio study

Using ab initio calculations, the cooperative and solvent effects on cation–π and B···N interactions are studied in some model ternary complexes, where these interactions coexist. The nature of the interactions and the mechanism of cooperativity are investigated by means of quantum theory of atoms in molecules (QTAIM), noncovalent interaction (NCI) index and natural bond orbital analysis. The results indicate that all cation–π and B···N binding distances in the ternary complexes are shorter than those of corresponding binary systems. The QTAIM analysis reveals that ternary complexes have higher electron density at their bond critical points relative to the corresponding binary complexes. In addition, according to the QTAIM analysis, the formation of cation–π interaction increases covalency of B···N bonds. The NCI analysis indicates that the cooperative effects in the ternary complexes make a shift in the location of the spike associated with each interaction, which can be regarded as an evidence for the reinforcement of both cation–π and B···N interactions in these systems. Solvent effects on the cooperativity of cation–π and B···N interactions are also investigated.     

Studies on the σ–hole bonds (halogen,chalcogen, pnicogen and carbon bonds) based on the orientation of crystal structure

ABSTRACT

The 4,7-dibromo-5,6-dinitro-2,1,3-benzothiadiazole (DDBT) crystal has two polymorphic forms [1 M.S. Pavan, A.K. Jana, S. Natarajan, and T.N. Guru Row, J. Phys. Chem. B 119, 11382 (2015).[Crossref], [PubMed], [Web of Science ®] , [Google Scholar]], where the close contacts between two electronegative atoms are identified and studied through Hirshfeld surface analysis. Br---Br and O---O cut-off distances are addressed and analysed. The σ–hole of bromine, sulphur, oxygen atoms and π-hole of carbon and nitrogen atoms were subjected to study using molecular electrostatic potential map and 3D-deformation density map. Sixteen types of dimers from the two forms of crystal structure (6 for form I and 10 for form II) were studied using the charge transfer properties and interaction energies and made detailed analysis of halogen bond (Br---N), dihalogen bond (Br---Br), chalcogen bond (O---Br and S---Br), dichalcogen bond (S---O, O---S and O---O), pnicogen bond (N---O) and carbon bond (C---O and C---Br) interactions. The impact of orientations is discussed to define the type of interaction and its strength through charge transfer mechanism. The contribution of bond angle values for the σ-hole and π–hole bonds are discussed. Utilisation of σ–hole in smaller bond angle values (above 30°) of |θ₁ ? θ₂| existing in type II halogen–halogen bond have been examined in the two forms.     

Theoretical study of the HXYH dimers (X,Y = O,S, Se). Hydrogen bonding and chalcogen–chalcogen interactions

A theoretical study of the HXYH (X, Y?=?O, S and Se) monomers and dimers has been carried out by means of MP2 computational methods. For the monomers, isomerization (H₂X=Y//HXYH) and rotational transition state barriers have been calculated. Additionally, the molecular electrostatic potential of the isolated monomers has also been analysed. Due to the chiral nature of these compounds, homo and heterochiral dimers have been explored. The number of minima found for the dimers range between 13 and 22. The electron density of the complexes has been characterized with the Atoms in Molecules (AIM) methodology finding a large variety of interactions. The DFT-SAPT method has been used to analyse the components of the interaction energies. Concerning chalcogen–chalcogen interactions, although the most stable minima are formed through hydrogen bonds (especially if OH groups are present in the molecules) as the size of the atoms involved in the interaction increase, the chalcogen–chalcogen contacts become more important.     

Characterization of Ag adsorption on TiC（001） substrate： an ab initio study

Ag adsorptions at 0.25-3 monolayer （ML） coverage on a perfect TIC（001） surface and at 0.25 ML coverage on C vacancy are separately investigated by using the pseudopotential-based density functional theory. The preferential adsorption sites and the adsorption-induced modifications of electronic structures of both the substrate and adsorbate are analysed. Through the analyses of adsorption energy, ideal work of separation, interface distance, projected local density of states, and the difference electron density, the characteristic evolution of the adatom-surface bonding as a function of the amount of deposited silver is studied. The nature of the Ag/TiC bonding changes as the coverage increases from 0.25 to 3 MLs. Unlike physisorption in an Ag/MgO system, polar covalent component contributes to the Ag/TiC interfacial adhesion in most cases, however, for the case of 1-3 ML coverage, an additional electrostatic interaction between the absorption layer and the substrate should be taken into account. The value of ideal work of separation, 1.55 J/m^2, for a 3-ML-thick adlayer accords well with other calculations. The calculations predict that Ag does not wet TIC（001） surface and prefers a three-dimensional growth mode in the absence of kinetic factor. This work reports on a clear site and coverage dependence of the measurable physical parameters, which would benefit the understanding of Ag/TiC（001） interface and the analysis of experimental data.     

A study on effect of sonochemistry in a reverberation field

In this paper,an ultrasound with frequency of 815 kHz was used to re-search the sonochemical yield in a small-size reverberation field by the methodof fluorescent spectrum analysis.There are two characteristics on the effect ofsonochemistry in the reverberation field:First,the cavitation threshold wasabout 0.3W/cm~2(it was 0.7W/cm~2 in travelling field);Second,when thesound intensity was larger than the threshold,the sonochemical yield increasedas the intensity increased and increased rapidly after the intensity was at1.69-2.13W/cm~2,so that there was a upturned point in the curve of the result(which would tend to saturation in the travelling field).The theoretical analysisshows that the reason of the threshold decrease is that the sound energy densitybecomes high in the reverberation field,and the upturned point results from thedisturbance of the radiation pressure on the liquid surface.Therefore,by exper-iment and theory this paper shows that a reverberation field has to be built forthe higher sonoche     

The effect of wavy leading edges on aerofoil–gust interaction noise

High-order accurate numerical simulations are performed to investigate the effects of wavy leading edges (WLEs) on aerofoil–gust interaction (AGI) noise. The present study is based on periodic velocity disturbances predominantly in streamwise and vertical directions that are mainly responsible for the surface pressure fluctuation of an aerofoil. In general, the present results show that WLEs lead to reduced AGI noise. It is found that the ratio of the wavy leading-edge peak-to-peak amplitude (LEA) to the longitudinal wavelength of the incident gust (_λg${\lambda }_g$) is the most important factor for the reduction of AGI noise. It is observed that there exists a tendency that the reduction of AGI noise increases with LEA/_λg$\mathrm{LEA}/{\lambda }_g$ and the noise reduction is significant for LEA/_λg≥0.3$\mathrm{LEA}/{\lambda }_g\ge 0.3$. The present results also suggest that any two different cases with the same LEA/_λg$\mathrm{LEA}/{\lambda }_g$ lead to a strong similarity in their profiles of noise reduction relative to the straight leading-edge case. The wavelength of wavy leading edges (LEW), however, shows minor influence on the reduction of AGI noise under the present gust profiles used. Nevertheless, the present results show that a meaningful improvement in noise reduction may be achieved when 1.0≤LEW/_λg≤1.5$1.0\le \mathrm{LEW}/{\lambda }_g\le 1.5$. In addition, it is found that the beneficial effects of WLEs are maintained for various flow incidence angles and aerofoil thicknesses. Also, the WLEs remain effective for gust profiles containing multiple frequency components. It is discovered in this paper that WLEs result in incoherent response time to the incident gust across the span, which results in a decreased level of surface pressure fluctuations, hence a reduced level of AGI noise.     

Structural,electronic and optical properties of ultrathin thallium nanowires – an ab initio study

The energetics and structural, electronic and optical absorption properties of thallium nanowires, Tl _n with n?=?1–18, have been investigated by employing a first-principles density functional theory in the local density approximation. The spin–orbit (SO) interaction has also been considered. We study four types of stable structures: planar, caged, pyramidal and helical. In general, the binding energy increases with the coordination number except in a few cases where the nearest-neighbours lie at comparatively larger separations. The maximum stability is seen for the helical configurations containing pentagons, hexagons, heptagons and octagons. Nanowires containing a core linear chain of atoms on the tube axis are more stable than the corresponding nanotubes having no such chains. All the wires or tubes are found to be metallic with or without consideration of the SO interaction. The electronic structures of the pentagonal-, hexagonal- and octagonal-configuration wires provide a large number of channels, which may give rise to large quantum ballistic conduction. One finds large differences between the optical absorption calculated with and without the SO interaction. Consideration of the SO interaction enhances the number of absorption peaks by approximately a factor of two. A strong and multi-peaked optical absorption, extending up to 4.0?eV including the visible region, appears for wires containing pentagons and octagons. These wires may thus be useful as a source of white radiation.     

Magneto-electronic properties and spin-resolved I–V curves of a Co/GeSe heterojunction diode: an ab initio study

We present ab initio calculations of magnetoelectronic and transport properties of the interface of hcp Cobalt (001) and the intrinsic narrow-gap semiconductor germanium selenide (GeSe). Using a norm-conserving pseudopotentials scheme within DFT, we first model the interface with a supercell approach and focus on the spin-resolved densities of states and the magnetic moment (spin and orbital components) at the different atomic layers that form the device. We also report a series of cuts (perpendicular to the plane of the heterojunction) of the electronic and spin densities showing a slight magnetization of the first layers of the semiconductor. Finally, we model the device with a different scheme: using semiinfinite electrodes connected to the heterojunction. These latter calculations are based upon a nonequilibrium Green’s function approach that allows us to explore the spin-resolved electronic transport under a bias voltage (spin-resolved I–V curves), revealing features of potential applicability in spintronics.     

Experimental and ab initio study of the nuclear quadrupole interaction of 181 Ta-probes in an α-Fe2O3 single crystal

We report perturbed-angular-correlation (PAC) experiments on ¹⁸¹Hf (→¹⁸¹Ta)-implanted corundum α-Fe₂O₃ single crystal in order to determine the magnitude, symmetry and orientation of the electric-field-gradient (EFG) tensor at Ta donor impurity sites of this semiconductor. These results are analyzed in the framework of ab initio full-potential augmented-plane wave plus local orbital (FP-APW+lo) calculations. This combined analysis enables us to quantify the magnitude of the lattice relaxations induced by the presence of the impurity and to determine the charge state of the impurity donor level introduced by Ta in the band gap of the semiconductor.     

The effect of local electronic interaction on the optical properties of boron–nitride nanotubes

We investigate the behavior of optical absorption of boron–nitride nanotubes (6,0) in the context of Hubbard model at the paramagnetic sector. GW approximation has been implemented in order to make self-energy matrix of electronic system. Afterwards, the real and imaginary parts of transverse dielectric functions have been obtained using linear response theory. The results show that the frequency gap in the optical absorption decreases with Coulomb repulsion strength. Moreover the results show that the local Coulomb interaction leads to the appearance of the excitonic effects in the optical spectrum. Finally the effects of electronic concentration on the frequency behavior of imaginary part of dielectric function have been investigated.     

The vibrations of glyoxal,studied by ‘Multimode’, with a large amplitude motion,using an ab initio potential surface

The procedure ‘Multimode’ was introduced by Carter and Bowman [1998, J. chem. Phys., 108, 43971, to calculate the vibrations of polyatomic molecules using normal coordinates. Recently Carter and Handy have introduced an extension to ‘Multimode’ to include one large amplitude torsional vibration for molecules for which an analytical potential is available. This procedure is now extended to molecules for which ab initio potential data may be calculated. Glyoxal (CHOCHO) is studied using the density functional approach to generate the potential surface data. The full J = 0 vibrational spectra is presented.     

The effects of bonding conditions on the propagation of acoustic waves along a cased borehole

1 IntroductionIn geophysical logging, one must study the soUnd field in cased borehole to properly assessthe case bonding conditions. Geophysicists have studied the sound fields in cased boreholesquite thoroughly and drawn many useful c.nclusionsll--6]. Bat they usually assume that thebonding conditions of the illterfaces between the case and cemellt, or between the cemellt andformation, are either well or poorly bonded. In the latter case, the bonding condition is modeledby a fluid annulus. …     

Ab initio study of the Ar–CS2(V1B2) intermolecular potential surface: effect of van der Waals interaction on the emission of CS2 molecule

In this work, the excited state intermolecular potential energy surface of the Ar–CS₂(V¹B₂) van der Waals complex was evaluated for the first time. The calculation of more than 4000 single-point interaction energies for the complex using an equation-of-motion coupled-cluster model with single and double substitutions level of theory with extended basis set involving bond functions has been performed. After fitting the interaction energies to analytical functions, the emission spectra of the Ar–CS₂(V¹B₂) complex related to the different stationary points on the potential energy surface were calculated. It was seen that the intensity and the position of the emission spectra are dependent on the orientation of the Ar atom around the bent excited CS₂ and the distance between two components. The information about the structural parameters of the complex related to the global minimum was obtained under the pseudodiatomic approximation with assistance of ab initio potential. The presented investigation could be useful for further theoretical and experimental studies of Ar–CS₂(V¹B₂) complex.     

Magnetization dynamics of mixed Co–Au chains on Cu(110) substrate:Combined ab initio and kinetic Monte Carlo study

We present an investigation of the one-dimensional ferromagnetism in Au–Co nanowires deposited on the Cu(110)surface. By using the density functional theory, the influence of the nonmagnetic copper substrate Cu(110) on the magnetic properties of the bimetallic Au–Co nanowires is studied. The results show the emergence of magnetic anisotropy in the supported Au–Co nanowires. The magnetic anisotropy energy has the same order of magnitude as the exchange interaction energy between Co atoms in the wire. Our electronic structure calculation reveals the emergence of new hybridized bands between Au and Co atoms and surface Cu atoms. The Curie temperature of the Au–Co wires is calculated by means of kinetic Monte Carlo simulation. The strong size effect of the Curie temperature is demonstrated.     

Enhancement effect of lithium bonding on the strength of pnicogen bonds: XH2P···NCLi···NCY as a working model (X = F,Cl; Y = H,F, Cl,CN)

MP2 calculations with aug-cc-pVDZ basis set were used to analyse intermolecular interactions in XH₂P···NCLi···NCY triads (X = F, Cl; Y = H, F, Cl, CN) which are connected via pnicogen bond and lithium bond. To understand the properties of the systems better, the corresponding dyads are also studied. Molecular geometries and interaction energies of dyads, and triads are investigated at the MP2/aug-cc-pVDZ computational level. Particular attention is paid to parameters such as cooperative energies and many-body interaction energies. All studied complexes, with the simultaneous presence of a lithium bond and a pnicogen bond, show cooperativity with energy values ranging between ?4.73 and ?8.88 kJ mol^?1. A linear correlation was found between the interaction energies and magnitude of the product of most positive and negative electrostatic potentials. According to energy decomposition analysis, it is revealed that the electrostatic interactions are the major source of the attraction in the title complexes.     

Optical switching in a Ξ system: A comparative study on DROP and EIT

Liquid Lennard-Jones clusters with magic number of atoms N = 55, 147, 309, 561 and 923 were cooled down in Monte Carlo simulations until freezing. Structural properties of the clusters, including the radial dependence of atomic concentration/density and the local regular structure in arrangement of atoms, just before freezing were analysed. Existence of spherical layers in atomic density around the centre of mass of liquid LJ clusters was confirmed. Formation of layers is explained by central net forces acting on every cluster atom and leading to positioning an atom close to the cluster centre of mass. The strong layering in small clusters of N = 55 and 147 affects atomic diffusion in radial and tangential directions inside the cluster, leading to easier movement of atoms on the layer surface. Analysis of radial profiles of four types of structural units detected in liquid clusters reveals that icosahedral units are the most numerous and are located mainly near cluster surface of all clusters and also in the centre of small clusters.