Interplay and competition between the lithium bonding and halogen bonding: R3C···XCN···LiCN and R3C···LiCN···XCN as a working model (R = H,CH3; X = Cl,Br)

UMP2 calculations with aug-cc-pVDZ basis set were used to analyse intermolecular interactions in R₃C···XCN···LiCN and R₃C···LiCN···XCN triads (R = H, CH₃; X = Cl, Br) which are connected via lithium bond and halogen bond. To understand the properties of the systems better, the corresponding dyads are also studied. Molecular geometries and binding energies of dyads, and triads are investigated at the UMP2/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 halogen bond, show cooperativity with energy values ranging between ?1.20 and ?7.71 kJ mol^?1. A linear correlation was found between the interaction energies and magnitude of the product of most positive and negative electrostatic potentials (V_S,maxV_S,min). The electronic properties of the complexes are analysed using parameters derived from the atoms in molecules (AIM) methodology. According to energy decomposition analysis, it is revealed that the electrostatic interactions are the major source of the attraction in the title complexes.     

Cooperative interaction between π-hole and single-electron σ-hole interactions in O2S···NCX···CH3 and O2Se···NCX···CH3 complexes (X = F,Cl, Br and I)

Ab initio calculations are performed to analyse the cooperative effects between π-hole and single-electron σ-hole interactions in O₂S···NCX···CH₃ and O₂Se···NCX···CH₃ complexes, where X = F, Cl, Br and I. These effects are investigated in terms of geometric and energetic features of the complexes, which are computed by UMP2/aug-cc-pVTZ(-PP) method. Our results indicate that the shortening of the each π-hole bond distance in the complexes is dependent on the strength of the σ-hole interaction. The maximum and minimum energetic cooperativity values correspond to the most and least stable complexes studied in the present work. The cooperativity between both types of interaction is chiefly caused by the electrostatic effects. The topological analysis, based on the quantum theory of atoms in molecules, is used to characterise the interactions and analyse their enhancement with varying electron density at bond critical points.     

Tuning of tetrel bonds interactions by substitution and cooperative effects in XH3Si···NCH···HM (X = H,F, Cl,Br; M = Li,Na, BeH and MgH) complexes

In this work, the interplay between the tetrel bond and the dihydrogen bond is investigated in ternary XH₃Si···NCH···HM complexes, where X = H, F, Cl, Br and M = Li, Na, BeH, MgH. The nature of Si···N and H···H interactions is studied by molecular electrostatic potential (MEP), noncovalent interaction and electron localisation function analyses. All binding distances in the ternary complexes are shorter than those of isolated XH₃Si···NCH and NCH···HM systems. That is, the two types of interactions have a cooperative effect on each other. The results of the MEP analysis indicate that the enhancement of the Si···N and H···H bonds can mainly be attributed to the electrostatic interaction. The plot of the reduced density gradient versus sign (λ₂)ρ indicates that the location of the spike associated with each interaction in the ternary systems moves slightly towards the negative (λ₂)ρ values with respect to the binary systems. This confirms that both Si···N and H···H interactions in the ternary complexes are strengthened by the presence of other. Besides, cooperative effects lead to a considerable change in the ¹⁴N nuclear quadrupole coupling constant values of the ternary complexes relative to the XH₃Si···NCH complexes.     

Synthesis,heating, and melting of stoichiometric glass (CaSiO3·SiO2)

Thermodynamic analysis (TERRA program) of synthesis, heating, and melting of stoichiometric glass CaSiO₃·SiO₂ has been carried out. Chemically pure substances silica and lime are subjected to exothermic reaction with further external heating and melting. Wollastonite is synthesized, the chemical reaction generates heat Q _chr = ?505.3 kJ/kg, and temperature increases T = 820 K. When T _melt = 1812–1814 K, wollastonite melts, and a mixture of liquid wollastonite and condensed silica is formed. At T _melt = 1995–1997 K, silica melts, and stoichiometric glass (CaSiO₃·SiO₂) is formed. Evolutions of temperature and melting of wollastonite and silica have been studied by detailed step-by-step thermodynamic calculation (ΔT = 0.1 K).     

Red, yellow, green and blue – four-color light from a single, aperiodically poled LiTaO3 crystal

We demonstrate simultaneous quasi-continuous wave generation of red, yellow, green and blue coherent radiation based on quadruple quasi-phase matching (QPM) frequency upconversion from a single, aperiodically poled LiTaO₃ (APPLT) crystal with a diode-pumped Nd:YVO₄ dual-wavelength laser oscillating at 1342 and 1064 nm. We designed and prepared an APPLT crystal, which can provide four pertinent reciprocals for simultaneous quadruple QPM processes. Namely, frequency doubling of 1342 nm generates red light at 671 nm, sum-frequency mixing of 1342 nm and 1064 nm produces yellow light at 593 nm, frequency doubling of 1064 nm achieves green light at 532 nm and sum-frequency mixing of 1342 nm and 671 nm obtains blue light at 447 nm. PACS 42.65.Ky; 42.79.Nv; 42.55.Xi; 42.72.Bj     

Blue and red shifts in Rg···HCN and Rg···HNC complexes (Rg=He,Ne, Ar,Kr)

The shift in the harmonic vibrational frequency of the H–C stretch of HCN on formation of the linear Rg···HCN complexes, and of the H–N stretch of HNC on the formation of Rg···HNC complexes (Rg?=?He, Ne, Ar, Kr), has been determined by ab initio computations. These shifts are in agreement with predictions from a model based on perturbation theory and involving the first and second derivatives of the interaction energy with respect to displacement of the H–C (H–N) bond length from its equilibrium value in the monomer. Small blue shifts were obtained for He···HCN, Ne···HCN and He···HNC, while red shifts were obtained for the other weakly bound complexes. These vibrational characteristics are rationalized by considering the balance between the interaction energy derivatives obtained from the perturbative model. For all complexes, the IR intensity of the H–C or H–N stretch was increased from the isolated monomer values on complexation.     

Electron spin resonance and structure of the ionic radical, ·PO3 =

It is shown that the ionic radical, ·PO₃ ⁼, is formed by the action of γ-rays on disodium ortho-phosphite pentahydrate. The hyperfine coupling to the ³¹P nucleus has principal values of 1967, 1514 and 1513 Mc/s and is consistent with a pyramidal ion having OPO angles of 110°.     

Theoretical investigation of the backbone···π and π···π stacking interactions in substituted-benzene||3-methyl-2′-deoxyadenosine: a perspective to the DNA repair

The π-stacking effects of substituted benzenes on the N-glycosidic bond strength of 3-methyl-2'-deoxyadenosine (3-MDA) were studied by quantum mechanical calculations. Although all substituents enhance the stacking interactions, enhancement is higher for the electron-donating (ED) substituents. When the overall binding energy is separated into the π···π (ΔE_π···π) and backbone···π (ΔE_bb···π) contributions, the ED and electron-withdrawing (EW) substituents increase those contributions, respectively. Both the ED and EW substituents decrease the distance between the centres of stacked rings, while the EW ones increase the N-glycosidic bond length. The electron charge density calculated at the C--N bond critical point (ρ_C–N) is in linear correlation with the backbone···π interaction, not with the π···π interaction. This study also shows that the charge transfer from X-Ben to 3-MDA is in linear correlation with the ΔE_π···π and the change in the charge on the sugar ring is in better accordance with the backbone···π interaction. The N7 proton affinity (PA_N7), with a key role in the depurination process, is highly affected by the π···π interactions. Thus, both interactions must be considered because of the balance between the backbone···π and π···π contributions in these biomolecular systems.     

Calculating Hamiltonian parameters for Yb^3＋ in a low-symmetry lattice site, and fitting the structure and levels of Yb^3＋ ：RETaO4 （RE = Gd, Y, and Sc）

An iterative method is used to find the values of the Hamiltonian parameters for Yb^3＋ in a given low-symmetry crys- talline site. Samples of Yb^3＋ ：RETaO4 （RE = Gd, Y, and Sc） were prepared and their structures were determined. Based on the obtained structural data, their orbital-spin parameters and crystal field parameters were fitted by the superposition model （SM）. Using the crystal field parameters obtained by the SM fitting as the initial parameters, the Hamiltonian parameters were fitted iteratively. The calculated and experimental energy levels for Yb^3＋：RETaO4 are consistent, and the maximal mean-root-square deviation is only 2.84 cm^- 1, indicating that the method is effective to determine the Hamiltonian parameters of Yb^3＋ in low-symmetry crystalline sites.     

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.     

Electronic structure, optical properties and lattice dynamics of MgSO3·6H2O

The electronic band structure, optical properties and lattice vibrations of MgSO(3)·6H(2)O were studied within density functional theory and compared to the experimental optical data and polarized Raman spectra. Due to the 'molecular' nature of the MgSO(3)·6H(2)O crystal all Γ-point phonon modes could be separated into groups belonging to specific structural blocks: Mg(H(2)O)(6) octahedra, SO(3) units and H(2)O molecules. All Raman lines in the experimental spectra are assigned to definite vibrations of the structure and reasonable agreement is found between theoretical and experimental mode frequencies. The temperature-dependent Raman spectra reveal at 60 °C a sharp transition from MgSO(3)·6H(2)O to anhydrous amorphous MgSO(3) without the noticeable presence of intermediate lower hydrates, such as MgSO(3)·3H(2)O.     

Electron Paramagnetic Resonance,Optical Spectra and DC Conductivity Studies of Vanadyl Doped Bi2O3 · BaO · B2O3 Glasses

Glasses with composition xBi₂O₃ ·(0.30 - x)BaO · 0.70B₂O₃ have been prepared in the range (0.00 ≤ x ≤ 0.15) containing 2.0 mol% of V₂O₅. Electron paramagnetic resonance (EPR), optical transmission and absorption spectra and DC conductivity of these glasses have been studied. The spin Hamiltonian parameters (SHP) of VO²⁺ ions, dipolar hyperfine coupling parameter P, Fermi contact interaction parameter K, and molecular orbital coefficients (α² and γ²) have been calculated. The SHP arc related with the theoretical optical basicity. A_th. The position of the absorption edge and the values of the optical band gap have also been reported. The effect of addition of Bi₂O₃ on the DC conductivity has also been studied.     

Defects,phase transitions and dynamical disorder in superionic protonic conductors H3OUO2PO4 · 3H2O and CsHSO4

Specific properties of the hydrogen bond and protons appear to be responsible for the formation of the quasi-liquid state of conducting ions and the resulting superionic behaviour. This state is reached by successive phase transitions involving the mobile species and their interactions with a more or less rigid framework. H₃OUO₂PO₄ · 3H₂O (HUP) and CsHSO₄ can be considered as models of wet and dry superionic conduction, respectively. Interactions between static effects and dynamical disorder as well as the coupling between sublattices are discussed in relation to results obtained by calorimetry, impedance spectroscopy (up to 10 GHz), vibrational spectroscopy and quasi-elastic neutron scattering.     

The prominent enhancing effect and mechanism of the methyl group in the X···Y (X=O,S, H3CO,H3CS, (H3C)2O, (H3C)2S; Y=HCN,HNC) hydrogen-bonded complex

An ab initio computational study of the enhancing role of the methyl group in the M···H (M=S and O) hydrogen bond has been carried out at the QCISD/6-311++G(2df,2p) level. The bond lengths, frequency shifts, and interaction energies were analysed. The methyl group of the electron donor plays a positive role in the formation of the hydrogen bond. Its enhancing role is stronger in the O···H hydrogen bond than in the S···H hydrogen bond. The results show that the methyl group has a prominent effect on the strength of the hydrogen bond. The interaction energy is increased by 347% for the Me₂O–HCN complex relative to that for the O–HCN complex. The enhancing mechanism of the methyl group has been analysed by means of natural bond orbital (NBO) theory. The electrostatic interaction is of more importance to the O···H hydrogen bond, whereas dispersion and charge-transfer interactions play a more significant role in the S···H hydrogen bond.     

Infrared spectra of acetylene dimers and acetylene–nitrogen: (DCCD)2, H-bonded DCCD–HCCH, and DCCD–NN in the 4.1 μm region

Infrared spectra of the weakly-bound T-shaped acetylene dimers DCCD–DCCD and DCCD–HCCH are studied in the region of the DCCD ν₃ fundamental (∼2440 cm⁻¹) using a pulsed supersonic slit-jet expansion and a tunable diode laser probe. The K_a = 0 ← 1 and 1 ← 0 subbands, corresponding to the vibration of the DCCD monomer at the “top” of the T, are analyzed. Compared to the analogous spectrum of HCCH–HCCH, the present results are much less perturbed. The tunneling splitting for (DCCD)₂ in the excited state is determined to be 141 MHz, a big reduction from the previously determined ground state value of 424 MHz. The dimer A rotational constants show a large apparent increase upon vibrational excitation, and we discuss whether this increase is real. The linear DCCD–NN complex is also observed as an impurity in the spectrum, and it too is found to be unperturbed, in contrast with HCCH–NN.     

Entanglement and Berry Phase in a (3×3)-dimensional Yang-Baxter System

A 9×9 unitary \breveR\breve{R} -matrix, solution of the Yang-Baxter Equation, is obtained in this paper. The entanglement properties of \breveR\breve{R} -matrix is investigated, and the arbitrary degree of entanglement for two-qutrit entangled states can be generated via \breveR\breve{R} -matrix acting on the standard basis. A Yang-Baxter Hamiltonian can be constructed from unitary \breveR\breve{R} -matrix. Then the geometric properties of this system is studied. The results showed that the Berry phase of this system can be represented under the framework of SU(2) algebra.     

Strengthening of the halogen-bonding by an aerogen bond interaction: substitution and cooperative effects in O3Z···NCX···NCY (Z = Ar,Kr, Xe; X = Cl,Br, I; Y = H,F, OH) complexes

The geometry, interaction energy and bonding properties of ternary complexes O₃Z···NCX···NCY (Z= Ar, Kr, Xe; X = Cl, Br, I and Y = H, F, OH) are investigated with ab initio calculations at the MP2/aug-cc-pVTZ level. Two different types of intermolecular interactions are present in these complexes, namely, aerogen bond (Z···N) and halogen bond (X···N). The formation mechanism and bonding properties of these complexes are analysed with molecular electrostatic potentials, quantum theory of atoms in molecules and non-covalent interaction index. It is found that the cooperativity energies in the ternary complexes are all negative; that is, the interaction energy of the ternary complex is greater (more negative) than the sum of the interaction energies of the corresponding binary systems. Also, the cooperativity energies increase with the increase of the interaction energies. The cooperative effects in the ternary complexes make a decrease in the total spin–spin coupling constants across the aerogen bonding, J(Z–N), which can be regarded as a proof for the reinforce of Z···N interactions in the ternary complexes with respect to the binary systems.