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.     

The mutual relationship between H-bonding and π-stacking interactions: the estimation of individual binding energies in the phenylalanine:G ··· C ternary complex

The mutual relationship between stacked interaction and the individual hydrogen bonds in the phenylalanine:guanine?···?cytosine (Ph:G-C) and phenylalanine:cytosine?···?guanine (Ph:C-G) complexes have been studied at the MPWB1K/6-311++G** and M05-2X/cc-pVDZ levels of theory. The interplay of π-stacking and H-bonding results in the weakening of both interactions. The effect of π-stacking on the geometries and individual hydrogen bond (HB) energies of guanine–cytosine (G-C) base pair have been investigated using electron densities calculated by the atoms in molecules (AIM) method at the hydrogen bond critical points (BCP). The results of AIM analysis are in good agreement with the calculated individual hydrogen bond energies. The π-stacking interactions strengths the HB1 and weakens HB2 and HB3 in the Ph:G-C complexes, while the opposite is true in the Ph:C-G complex. With the increase in the distance between phenylalanine ring and the groups involved in H-bond interactions the change in the H-bond energy increases and the changes in the individual H-bond and π-stacking energies decrease in the ternary complexes.     

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.     

Prediction of binding bond energy between phosphorous-based ionic liquids and CO2. Assessment of the CO2–anion interactions

The absorption of carbon dioxide (CO₂) in phosphorous-based ionic liquids was studied theoretically by the molecular modeling ab initio density functional theory (dispersion-corrected B3LYP) and second-order M?ller-Plesset perturbation methods. Several types of phosphate- and phosphite-based anions were employed and the calculation results were compared with recent published papers. The interaction energy between CO₂ and anion, following the result of Bhargava and Balasubramanian, was calculated in order to have a better understanding on the effect of different functional groups on the interaction between CO₂ and anion. The computational results indicated that the molar volume of the anion molecules played an important role on the absorption mechanism of CO₂ due to the CO₂-philicity of carbonyl and alkyl groups.     

Relationship between electromagnetically-induced transparency and Autler–Townes splitting in a Doppler-broadened system

We study the relationship between electromagnetically-induced transparency(EIT) and Autler–Townes(AT) splitting in a cascade three-level Doppler-broadened system. By comparing the absorption spectrum with the fluorescence excitation spectrum, it is found that for a Doppler-broadened system, EIT resonance cannot be explained as the result of quantum interference, unlike the case of a homogeneously broadened system. Instead, the macroscopic polarization interference plays an important role in determining the spectra of EIT and AT splitting, which can be explained within the same framework when being detected by the absorption spectra.     

Relation between the fine structure of the vibrational spectrum of the crystal lattice and the cation distribution in Co1+2xFe2−3xSbxO4 ferrites

The infrared reflection spectra in the region of lattice vibrations (1500–200 cm^–1) of ferrite spinels Co_1+2xFe_2–3xSb_xO₄ with x=0.0–0.4 are investigated. The permittivity spectra are calculated using the Kramers-Kronig relations. A dispersion analysis of the ₁(v); ₂(v) spectra, carried out using the multiscintillator model, enabled the fine structure of the bands of the spectra to be determined. It was found that for CoFe₂O₄ ferrite the short-wave band (v=590 cm^–1) consists of two components, while the long-wave band (v=375 cm^–1) consists of fur components. Since cobalt ferrite is inverted spinel, in which there are only Fe³⁺ ions in the tetra positions, the doublet structure with v=590 cm^–1 must obviously belong to vibrations of the ion groups FeO₆ and CoO₆, while the second band may belong to vibrations of the ion complexes consisting of the tetra-cation (Fe³⁺), oxygen and the three closest octa-cations [3Fe], [2Fe1Co], [2Co1Fe] and [3Co]. The replacement of some of the iron ions with antimony leads to the appearance of additional lines from the short-wave edge of both bands. The intensity of these lines increases as the value of the diamagnetic substitution increases, which enables the highest-frequency component to be uniquely related to the vibrations of the complex formed by the tetra-cations Fe³⁺ or Co²⁺, the anion and the three octa-cations Sb⁵⁺.V. I. Ul'yanov-Lenin Kazan State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 105–109, July, 1995.     

Spin-orbit coupling and the dynamic Jahn-Teller effect in the C 60 − system

The dynamic Jahn-Teller effect is studied for a charged fullerene molecule C ₆₀ ⁻ with allowance for spin-orbit coupling. The system of self-consistent equations describing the interaction of an electron and the molecular vibrations in the event of spin-orbit splitting of the electronic level is solved analytically. A novel type of nonlinear vibrations occurring in such a system is described. It is shown that with spin-orbit coupling taken into account, the static Jahn-Teller configurations in the C ₆₀ ⁻ molecule are unstable even in the limit of strong electron-vibronc coupling and that the symmetry of the atomic configuration of the unperturbed C ₆₀ ⁻ molecule is restored under time averaging. Zh. éksp. Teor. Fiz. 116, 194–203 (July 1999)     

High-precision laser and RF spectroscopy of the spin-rotation and HFS interactions in the X2Σ+ and B2Σ+ states of LaO

The spin-rotation and hyperfine interactions in the X²Σ⁺ and B²Σ⁺ electronic states of ¹³⁹La¹⁶O have been studied using Doppler-free laser-induced fluorescence and molecular-beam laser-rf double resonance. Observations were made for several values of v and many values of N, allowing evaluation of the principal interaction strengths and their N and v dependences for both the X and B states. The results are compared with earlier results for the isoelectronic system ¹³⁷Ba¹⁹F.     

A study of the α-transfer reaction in the 16O + 16O system at near-barrier energies

Excitation functions and angular distributions have been measured at energies near the Coulomb barrier for the elastic scattering of ¹⁶O from ¹⁶O and for the (¹⁶O, ¹²C) α-transfer reaction to the ground state and first excited state of ²⁰Ne. No evidence for (quasi-molecular) resonances was found in the transfer excitation functions. Exact-finite-range DWBA calculations were performed employing double-folded real and Woods-Saxon optical potentials for the distorted waves. The α-transfer reaction was found to be sensitive to the choice of the optical potential and generally better fits were obtained with the folded potentials.     

Calculation of the binding energy and of the parameters of low-energy scattering in the Λnp system

The cluster-reduction method is used to solve the differential Faddeev equations for S=1/2, T=0 and S=3/2, T=0 spin-isospin states of the Λnp system in the s-wave approximation. The NN interaction is simulated on the basis of the MT I–III potential model, and the ΛN potential is set to V _ΛN =V _NN /2. This simple option makes it possible to reproduce faithfully the binding energy of the hypertriton _Λ ³ H. The doublet and quadruplet Λd scattering lengths and the low-energy phase shifts are calculated. It is shown that the effective-range approximation is applicable to the cases of doublet and quadruplet scattering.     

On the binding energies and configurations of vacancy and copper–vacancy clusters in bcc Fe–Cu:a computational study

The properties of trapping centres in – as grown – Tl₄GaIn₃S₈ layered single crystals were investigated in the temperature range of 10–300 K using thermoluminescence (TL) measurements. TL curve was analysed to characterize the defects responsible for the observed peaks. Thermal activation energies of the trapping centres were determined using various methods: curve fitting, initial rise and peak shape methods. The results indicated that the peak observed in the low-temperature region composed of many overlapped peaks corresponding to distributed trapping centres in the crystal structure. The apparent thermal energies of the distributed traps were observed to be shifted from ~12 to ~125 meV by increasing the illumination temperature from 10 to 36 K. The analysis revealed that the first-order kinetics (slow retrapping) obeys for deeper level located at 292 meV.     

Benchmark CCSD(T) and DFT study of binding energies in Be7 − 12: in search of reliable DFT functional for beryllium clusters

We present a computational study of the stability of small homonuclear beryllium clusters Be_{7 ? 12} in singlet electronic states. Our predictions are based on highly correlated CCSD(T) coupled cluster calculations. Basis set convergence towards the complete basis set limit as well as the role of the 1s core electron correlation are carefully examined. Our CCSD(T) data for binding energies of Be_{7 ? 12} clusters serve as a benchmark for performance assessment of several density functional theory (DFT) methods frequently used in beryllium cluster chemistry. We observe that, from Be₁₀ clusters on, the deviation from CCSD(T) benchmarks is stable with respect to size, and fluctuating within 0.02 eV error bar for most examined functionals. This opens up the possibility of scaling the DFT binding energies for large Be clusters using CCSD(T) benchmark values for smaller clusters. We also tried to find analogies between the performance of DFT functionals for Be clusters and for the valence-isoelectronic Mg clusters investigated recently in Truhlar's group. We conclude that it is difficult to find DFT functionals that perform reasonably well for both beryllium and magnesium clusters. Out of 12 functionals examined, only the M06-2X functional gives reasonably accurate and balanced binding energies for both Be and Mg clusters.     

Phase differences between quantum oscillations of the magnetoresistance and the hall effect in Hg1−xMnxTe and Hg1−xCdxTe

A Landau-level broadening-dependent phase shift has been observed between the Shubnikovde Haas oscillations of the magnetoresistance and the Hall effect in a series of Hg_1−xMn_xTe and Hg_1−xCd_xTe samples. The phase shift varies between 0 and 90° and appears not to be influenced by the exchange interaction between the Mn²⁺ ions and the carriers. The results are in good agreement with the theoretical predictions for short range scattering potentials.     

The discrepancy between τ and e + e − spectral functions revisited and the consequences for the muon magnetic anomaly

We revisit the procedure for comparing the π π spectral function measured in τ decays to that obtained in e ⁺ e ^? annihilation. We re-examine the isospin-breaking corrections using new experimental and theoretical input and find improved agreement between the τ ^?→π ^? π ⁰ ν _τ branching fraction measurement and its prediction using the isospin-breaking-corrected e ⁺ e ^?→π ⁺ π ^? spectral function, though not resolving all discrepancies. We recompute the lowest order hadronic contributions to the muon g?2 using e ⁺ e ^? and τ data with the new corrections and find a reduced difference between the two evaluations. The new tau-based estimate of the muon magnetic anomaly is found to be 1.9 standard deviations lower than the direct measurement.     

Vibrational Analysis of the A3Π0−X1Σ+ and B3Π1−X1Σ+ Subsystems of the GaBr Molecule

Abstract

The emission band spectrum of gallium monobromide has been excited in a dc hollow cathode discharge. bands of the ³Π_0,1?X¹Σ⁺ system, lying in the range from 340 to 370 nm have been recorded at high resolution and measured. The previous vibrational analysis has been revised and corrected. New vibrational assignment has been proposed and improved vibrational constants of the upper and lower electronic states have been determined.     

Study of the production of a strange (S = −1) dibaryon in the interactions of K− and π+ on deuterium below 1.5GeV/c

The production of a strange dibaryonic system called H⁺₁ (M = 2.13 GeV/c², S = ?1), has been studied with a missing mass spectrometer, at the CERN Proton Synchrotron, in the reaction K^?d → π^?H⁺₁ and in the line-reversed reaction π⁺d → K⁺H⁺₁ between 0.9 and 1.4 GeV/c.The reactions

$\text{K}{}^{\mathrm{?}}\text{d}\text{→ π}{}^{\mathrm{?}}\text{X}{}^{\mathrm{+}}$

,

$\text{π}{}^{\mathrm{<mtext>d</mtext>}}\text{→}\text{K}{}^{\mathrm{+}}\text{X}{}^{\mathrm{+}}$

,have been studied in a missing mass spectrometer at CERN. The experiment (PS159) is well adapted to search for a signal in the missing mass X⁺ (B = 2, S = ?1) produced in the backward c.m.s. direction, between 2.0 and 2.3 GeV/c². The two reactions have been analysed at three different beam settings: 1.4, 1.06 and 0.92 GeV/c for reaction (1) and 1.4, 1.2 and 1.06 GeV/c for reaction (2).     

Local defect structures and EPR studies on (FeO6)9− and (FeO4)5− clusters in YGG: Fe3+ system

The octahedral (FeO₆)^9? and tetrahedral (FeO₄)^5? clusters in yttrium gallium garnet (YGG): Fe³⁺ system are investigated based on the 252 × 252 complete energy matrices for d⁵ configuration ions in trigonal and tetragonal ligand fields, moreover, the EPR and optical spectra are made unified calculation. The results indicate that the defect structures around Fe³⁺ centres display expansion effects at different temperatures 4.2 and 295 K, and which are close to those in YIG garnet, respectively. Simultaneously, the defect structure parameters for Fe³⁺ centres in YGG are determined, and the relationship between the defect structure and the temperature has been discussed.