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.     

Theoretical study on cooperative interplay between anion–π and chalcogen-bonding interactions

The mutual influence between anion–π and chalcogen bond interactions is studied by ab initio calculations at the MP2/6-311++G^** level of theory. These effects are analysed in detail in terms of the structural, energetic, charge-transfer and electron density properties of the complexes. Interesting cooperativity effects are found when anion–π and chalcogen-bonding interactions coexist in the same complex. The effect of anion–π on the properties of chalcogen bonding is larger than that of chalcogen bonding on the properties of anion–π. The cooperative mechanism is analysed in terms of the electrostatic potentials, orbital interaction and electron density analysis.     

Novel 0–π transitions in Josephson junctions between noncentrosymmetric superconductors

We study the Josephson effect between two noncentrosymmetric superconductors(NCSs) with opposite polarization vectors of Rashba spin–orbit coupling(RSOC).We find a 0–π transition driven by the triplet–singlet ratio of NCSs.Different from conventional 0–π transitions,the Andreev bound states change their energy range instead of phase shift in the 0–π transition found here.This novel property results in a feature that the critical current becomes almost zero at the transition point,not only a minimum.Furthermore,when the directions of RSOC polarization vectors are the same in two NCSs,the similar effect can also be found in the presence of a perpendicular exchange field or a Dresselhause spin–orbit coupling in the interlayer.We find novel oscillations of critical current without 0–π transition.These novel 0–π transitions or oscillations of critical current present new understanding of the Josephson effect and can also serve as a tool to determine the unknown triplet–singlet ratio of NCSs.     

The triel bond: a potential force for tuning anion–π interactions

Using ab-initio calculations, the mutual influence between anion–π and B···N or B···C triel bond interactions is investigated in some model complexes. The properties of these complexes are studied by molecular electrostatic potential, noncovalent interaction index, quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. According to the results, the formation of B···N or B···C triel bond interactions in the multi-component systems makes a significant shortening of anion–π distance. Such remarkable variation in the anion–π distances has not been reported previously. The strengthening of the anion–π bonding in the multi-component systems depend significantly on the nature of the anion, and it becomes larger in the order Br^? > Cl^? > F^?. The parameters derived from the QTAIM and NBO methodologies are used to study the mechanism of the cooperativity between the anion–π and triel bond interactions in the multi-component complexes.     

The 0–π Phase Transition in Epitaxial NbN/Ni_(60)Cu_(40)/NbN Josephson Junctions

We fabricate high quality superconductor/ferromagnet/superconductor(SFS) Josephson junctions using epitaxial NbN/Ni_(60)Cu_(40)/NbN trilayer heterostructures. Both experimental measurements and theoretical calculations of the ferromagnet layer thickness dependence of the Josephson critical current are performed. We observe the damped oscillation behavior of the critical current as a function of the ferromagnetic layer thickness at 4.2 K,which shows a 0–π phase transition in this type of magnetic Josephson junction. Clear 0– and reverse –0 phase transitions occur around the Ni_(60)Cu_(40) thicknesses of 3.2 and 6.7 nm. Numerical calculations based on the quasi-classical Usadel equation and the Green function fit well with the experimental results. Compared with the dirty limit, the intermediate regime without the dead layer gives better fit for our SFS Josephson junctions because of the epitaxial structure. Both of the 0-and -phase junctions show the ideal magnetic field dependence with a Fraunhofer-like pattern at 4.2 K.     

The strengthening effect of a halogen,chalcogen or pnicogen bonding on halogen–π interaction: a comparative ab initio study

The aim of this work is to study the possible cooperative effects between Z···N and X···π interactions (Z = Cl, S, P and X = Cl, Br) in some model complexes, where both these interactions coexist. The nature of the interactions in these complexes is characterised by means of molecular electrostatic potential, electron localisation function, quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. According to the results, the formation of an Z···N interaction in these systems makes a significant shortening of X···π distance. The cooperative enhancement of the X···π bonding in the ternary complexes depend on the strength of the Z···N interaction, and it becomes larger in the order Z = Cl > S > P. The mechanism of the cooperativity between the Z···N and X···π interactions is studied using the parameters derived from the QTAIM and NBO analyses.     

Interplay between the intramolecular hydrogen bonds and cation–π interactions in various complexes of salicylaldehyde,thiosalicylaldehyde and selenosalicylaldehyde with Li+, Na+, K+, Mg2+ and Ca2+ cations

For the first time, the mutual influences of the intramolecular hydrogen bond (IMHB) and cation–π interactions in various complexes of salicylaldehyde, thiosalicylaldehyde and selenosalicylaldehyde with Li⁺, Na⁺, K⁺, Mg²⁺ and Ca²⁺ cations were studied. First, the strength of IMHB and cation–π interactions of the mentioned complexes by energetic, geometrical, spectroscopic, topological and molecular orbital parameters was evaluated and compared with the corresponding results of benzene–cation complexes and salicylaldehyde analogues. The results show that the coexistence of IMHB and cation–π interactions increases the IMHB strength and decreases the cation–π interactions. Second, the significance of π–electron delocalisation (π–ED) within the resonance-assisted hydrogen bond (RAHB) unit and aromaticity of benzene ring in the studied complexes were estimated by using the harmonic oscillator model of aromaticity and compared with the respective amounts of references. The results indicated that the mentioned coupling decreases the π–ED of RAHB unit and aromaticity of the benzene ring. In addition, it was found that variations in the strength of the interactions, π–ED and aromaticity, depend on the charge-to-radius ratio of cations. Finally, the effects of replacement of O by S and Se atoms in both of the mentioned cases were explored.     

A computational study of interplay between hydride bonding and cation–π interactions: H-Mg-H···X···Y triads (X = Li+, Na+, Y = C2H2, C2H4, C6H6) as model systems

In the present study, H-Mg-H···X···Y (X = Li⁺, Na⁺ and Y = C₂H₂, C₂H₄, C₆H₆) triads have been investigated at MP2/6-311++G(2d,2p) computational level to characterise cooperative effects between hydride bonding and cation–π interactions. Molecular geometries, binding energies, cooperative energies and many-body interaction energies were evaluated. The diminutive energy values in triads with Li⁺ are larger than respective values in triads with Na⁺. The electronic properties of the complexes are analysed using parameters derived from the quantum theory of atoms in molecules methodology.     

Ab initio study of synergetic effects of two strong interactions of cation–π interaction and lithium bond in M+ ··· phenyl lithium ··· N (M = Li,Na, K; N = H2O and NH3) complex

Quantum chemical calculations have been performed to investigate the interplay between the cation–π interaction and lithium bonding in the M⁺?···?phenyl lithium?···?OH₂ and M⁺?···?phenyl lithium?···?NH₃ (M?=?Li, Na, K) complexes. The cation–π interaction and lithium bonding in the trimers become stronger relative to the dimers. The interaction energy of cation–π interaction is increased by about 4.4–6.3%, while that of lithium bonding is increased by about 5.2–15.9%. The cooperative energy becomes larger for the stronger cation–π interaction and lithium bond. The F atom and methyl group in the phenyl ring impose a reverse effect on the cation–π interaction and lithium bond. The interaction mechanism in the complexes has been understood with the many-body interaction analysis, electrostatic potentials, and energy decomposition.