Selectivity in the aggregates of the chiral organolithium N-Boc-2-lithiopiperidine with a chiral ligand: a DFT study

In this paper the aggregates of the chiral organolithium N-Boc-2-lithiopiperidine [Boc=CO₂C(CH₃)₃], which play an important role in the formation of chiral 2-substituted piperidines found in many alkaloid structures and medicinal compounds, have been investigated within the framework of Density Functional Theory (DFT) calculations. In the complex structures, the lithium atoms are tetra-coordinated, the diaminoalkoxide ligand is tridentate to one lithium atom and forms a chelate with the substrate which is stabilized by the solvent diethyl ether. The same type of bonding was observed for all the different ligand-bound structures; for ligands 6 and 7, which have bulky substituents, selectivity was in agreement with experiment. The results shed light on the microscopic structures of these species and suggest a potential ligand, 11, to yield high enantioselectivity.     

Theoretical study of the [Si,C, P,O] potential energy surface

The structures, energetics, spectroscopies and stability of the doublet [Si, C, P, O] radical are explored at the density functional theory and ab initio levels. Eighteen isomers connected by 22 interconversion transition states are located at the DFT/B3LYP/6-311G(d) level. The structures of the kinetically stable isomers and the relevant transition states are further optimized at the QCISD/6-311G(d) level followed by CCSD(T)/6-311 + G(2df) single-point energy calculations. At the QCISD/6-311G(d) level, the lowest-lying isomer is the cyclic O-cCSiP 8 (0.0 kcal/mol) with considerable kinetic stability of 22.0 kcal/mol. In addition, two bent isomers OSiCP 1 (7.3 kcal/mol) and SiCPO 3 (34.7 kcal/mol) also possess considerable kinetic stability (more than 10.0 kcal/mol). As a result, three isomers 1, 3 and 8 are predicted to be possible candidates for future experimental and astrophysical detection. The bonding nature of the three isomers is analysed. The calculated results are compared with those of the analogous radical [Si, C, N, O]. Implications in the laboratory and interstellar space are also discussed. The predicted structures and spectroscopic properties are expected to be informative for the identification of [Si, C, P, O] in the laboratory and space.     

Theoretical investigation on structures,stability and properties of [P,X, Y] (X=C,Si; Y = O,S) isomers

The structures, energetics and stability of the [P, X, Y] (X?=?C, Si; Y?=?O, S) radicals are explored by means of the density functional theory and ab initio levels. Seventeen [P, X, Y] isomers and 14 interconversion transition states are obtained at the B3LYP/6-311G(d) level. At the CCSD(T)/6-311?+?G(2df)//QCISD/6-311G(d)?+?ZPVE level, the lowest-lying isomers are the linear PCO 1a (0.0?kcal/mol), PCS 1b (0.0) and the three-membered ring cPSiO 1c (0.0), cPSiS 1d (0.0) on their respective potential energy surfaces. These four isomers exhibit considerably not only thermodynamic but also kinetic stabilities. Additionally, the cyclic cPCS 2b (32.8) and linear PSiS 2d (18.6) possess also high kinetic stability. All of six isomers 1a, 1b, 2b, 1c, 1d and 2d are considerably stabilized by a barrier of at least 20?kcal/mol, and may be detected in the laboratory or interstellar space. Their valence bond structures and possible formation strategies in the laboratory and space are discussed in detail. Finally, the similarities and discrepancies on structures and stabilities between [P, X, Y] (X?=?C, Si; Y?=?O, S) isomers are compared. These predicted results are highly expected to be informative for the future identification of [P, X, Y] (X?=?C, Si; Y?=?O, S) in the laboratory and space.     

The Al-Pd-Mn quasicrystalline approximant -phase revisited

A detailed investigation of the Fourier space of several Al-Pd-Mn samples with composition Al-72.6 at. %, Pd-22.9 at. %, Mn-4.5 at. % is reported. In the phase diagram of the Al-Pd-Mn ternary alloy, this composition corresponds to the so-called ξ' phase which was described as an icosahedral quasicrystalline approximant. By re-examining the Fourier space by means of X-ray diffraction (powder patterns and single crystal precession patterns), complex structures in close relation with the ξ'-phase have been observed. These long-range order complex structures are described as resulting from a periodic perturbation of the ξ' structure along the c direction. Two states with periodicities c (3 + τ) and c (5 + τ) have been observed in this study (τ: golden mean). Structural models based on periodic arrangements of “defects” layers separating layers of phase are proposed. These two states are certainly intermediate states between the phase and the metastable decagonal quasicrystalline phase. Received 11 April 2002 / Received in final form 24 June 2002 Published online 17 September 2002     

Structures and stability of N13 cluster

Quantum chemical studies for the nine N₁₃ isomers with low spin were carried out at the UHF/6-31G*, UB3LYP/6-31G* and UMP2/6-311G* levels of theory. The most stable N₁₃ isomer is structure 1 with C_2v symmetry, which contains two separated pentazole rings connected by three nitrogen atoms. The results show that structures 1, 2, 3, 4 and 5 which are composed of the pentazole ring are more stable than the open chain structure 6 and structures 8 and 9 which contain the four- and six-membered rings. This suggests that the pentazole ring is a fundamental stable structural unit, which is applicable not only for the even-numbered nitrogen clusters, but also for the large odd-numbered clusters.     

A chiral axial next nearest neighbour xy-model for antiferroelectric liquid crystals

We describe a chiral axial next nearest neighbour xy-model to account for the various subphases exhibited by antiferroelectric liquid crystals made of chiral rod-like molecules. The assumed form of the interlayer interactions is based on physical processes which are discussed. Using a discrete model, the predicted sequence of transitions is SmA-SmC-SmC-FI_H-FI_I-FI_L-SmC ^* A, where FI stands for a ferriphase, as seen in many compounds. The ferri and SmC phases are characterized by relatively large angles between the c-vectors of successive layers and occur only when the compounds have high optical purity. The calculated field induced structures exhibit a plateau of the apparent tilt angle at , where is the tilt angle of the molecules in the ferriphase. The conoscopic figures in the presence of a field and ellipsometric parameters in the absence of a field have also been generated, which agree extremely well with the experimental results. Recent anomalous X-ray scattering studies prove the xy-character of the configurations, though the commensurate structures that are found in the ferriphase require an extension of the model to include lock-in terms. Received 23 August 1999     

Inelastic resonant tunneling

A general expression for the resonant contribution to a tunneling current has been obtained and analyzed in the tunneling Hamiltonian approximation. Two types of resonant tunneling structures are considered: structures with a random impurity distribution and double-barrier structures, where the resonant level results from size quantization. The effect of temperature on the current-voltage curves of tunneling structures is discussed. The study of the effect of potential barrier profile on the d ² I/dV ² line shape is of interest for experiments in inelastic tunneling spectroscopy. Various experimental situations where the inelastic component of the tunneling current can become comparable to the elastic one are discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 1151–1155 (June 1998)     

Prediction of the linear and nonlinear optical properties of tetrahydronaphthalone derivatives via long-range corrected hybrid functionals

The linear and nonlinear optical (NLO) properties of methoxybenzylidene (1) and thiophen-2-ylmethylidene (2) tetrahydronaphthalone derivatives are studied using long-range corrected density functional theory (LC-DFT). The calculated hyperpolarisabilities indicate that both compounds have measurable NLO properties (approximately one to two times the hyperpolarisability of p-nitroaniline). Charge-transfer indices and time-dependent DFT calculations suggest that the NLO properties are a result of a charge-transfer excitation, which is typical in conjugated donor–acceptor structures. The ultraviolet–visible spectra of 1 and 2 are also predicted using gap-fitting schemes, and these data are used to assess how accurately the hyperpolarisabilities of 1 and 2 could be estimated by the solvatochromic method.     

Dihydrogen bond in C2H4− n Cl n ··· NaH (n = 0, 1, 2, 3) complexes: ab initio,AIM and NBO studies

The dihydrogen-bonded complexes of ethylene and its chlorine derivatives with sodium hydride have been systematically investigated at the MP2/6-311++G(d,p) level. The studied complexes are divided into three groups (including Linear, Five- and Six-membered cyclic structures) based on the optimized structures. The structural, energetic and topological parameters are presented and analysed in terms of their possible correlation with the interaction energies and the intermolecular H?···?H distances. The nature of the electrostatic interaction in this type of dihydrogen bond has also been unveiled by means of atoms in molecules (AIM) and natural bond orbital (NBO) analysis. The effect of ring structure on the dihydrogen bonding systems has been considered by comparing with the corresponding linear structure. NBO analysis suggests that the electron density transfer (EDT) in cyclic structures have dual-channel character.     

Structures and thermoelectric convection in cholesteric liquid crystals

The possibilities for excitation of electromagnetic field structures and convection cells, i.e., temperature and velocity structures, in a thermotropic cholesteric liquid crystal in the presence of flow are studied. Estimates are made and possible experiments for observing such structures are discussed. A special thermoelectric effect is investigated as the cause of these excitations — the influence of a heating-induced change in the pitch of the cholesteric helix of the molecules on the permittivity and the electric conductivity of the material. Fiz. Tverd. Tela (St. Petersburg) 41, 165–170 (January 1999)     

Magnetic phases in Mn<Subscript>1</Subscript>_<Subscript>x</Subscript>Fe<Subscript>x</Subscript>WO<Subscript>4</Subscript> studied by neutron powder diffraction

The magnetic structures of Mn_1-xFe_xWO₄ with x = 0.0, 0.16, 0.21, 0.225, 0.232, 0.24, 0.27, 0.29, and 1.0 were refined from neutron powder diffraction data. The magnetic phase diagram could be completed in the coexistence range of different magnetic structures up to x = 0.29. For the magnetic state at 1.5 K a commensurate antiferromagnetic structure with a propagation vector = (±1/4, 1/2, 1/2) was found for x ⩽ 0.22 while the magnetic spins order with = (1/2, 0, 0) for x ≥ 0.22. In the latter phase, additionally, weak magnetic reflections indexed to an incommensurate ordering with = (- 0.214, 1/2, 0.457) occur in the diffraction pattern up to x = 0.29 indicating the occurence of a reentrant phase. For 0.12 ⩽ x ⩽ 0.29 the low temperature phases are separated from a magnetic high temperature phase showing only magnetic reflections indexed to a spin arrangement with = (1/2, 0, 0). The magnetic phase diagram is discussed qualitatively considering random superexchange between the statistically distributed Mn²⁺- and Fe²⁺-ions in the coexistence range 0.12 ⩽ x ⩽ 0.29 of different magnetic structures related to those of pure MnWO₄ and FeWO₄. Received 9 October 2002 Published online 14 March 2003     

Optical Filters Using Optical Multi-Layer Structures for Optical Communication Systems

Abstract

In this article, light reflection spectrums for different one-dimensional multi-layer structures are obtained. Optical reflectivities for periodic, superperiodic, and quasiperiodic structures have been calculated using the transfer matrix method. PBGs of each structure have been obtained using the optical reflectivity pattern. From a comparison of reflectivity and standard dense wavelength division multiplexing grids, it is demonstrated that narrow and dense band filters can be built from generalized Fibonacci quasiperiodic structures. Reflectivity of these structures contains bands that meet the ITU-T dense wavelength division multiplexing standard. Reflectivity of other multi-layer structures has poor or less potential to be used in dense wavelength division multiplexing systems.     

Computational reconstitution of crystal structures and (p,T) phase diagrams of benzene C6H6 and hexachlorobenzene C6Cl6

Abstract

With a simplified dynamical model for molecular packing analysis, crystal and molecular structures of benzene C₆H₆ and hexachlorobenzene C₆H₆ were investigated. This model includes thermal motion and molecular deformation effects. Several crystalline structures have been found by the calculation. They are compared to experimental structures determined at various temperatures and pressures, by X-ray diffraction or neutron scattering. A schematic (p, T) phase diagram is suggested for each compound.     

Electric fields in dielectric structures with nonuniformly distributed surface charges

The distribution of the potential and intensity of the electric field in dielectric structures with a nonuniform surface charge is analyzed. Computational formulas are proposed and computational results are presented. Zh. Tekh. Fiz. 69, 138–140 (August 1999)     

Electron-ion interactions in close packed metals

The electron-ion interactions are evaluated exactly over the actual shape of the atomic polyhedron by making use of simple co-ordinate axes transformations and lattice symmetry in the case of hcp and ccp structures. It is shown that the expressions for the interference factor,S(q,t) of hcp structure are complex while those of ccp structure are real, even when both atomic arrangements are referred to the same orthorhombic co-ordinate axes, and in each case, lattice atom contributions could be distinguished from basis atom contributions toS(q,t). By comparing these expressions with each other as well as with those obtained by approximating their atomic polyhedra by an ellipsoid of equivalent volume, apparent differences between interference factors of hcp and ccp structures, validity of Wigner-Seitz approximation for a diatomic lattice and the manner in which the electron-ion interactions contribute to the different modes of vibration in a hexagonal lattice are discussed.     

Density functional theory studies of screw dislocation core structures in bcc metals

The core structures of d111 screw dislocations in bcc metals are studied using density functional theory in the local-density approximation. For Mo and Fe, direct calculations of the core structures show the cores to be symmetric with respect to 180 rotations around an axis perpendicular to the dislocation line. The magnetic moment in the Fe core is shown to be reduced relative to the bulk value. Calculations of nsurfaces and the elastic constants B , C ' and c 44 are reported for Fe and all group VB and VIB metals. Using a criterion suggested by Vitek and Duesbery the calculations point to symmetric core structures for all the studied metals.     

Formation of cold Cs ground state molecules through photoassociation in the pure long-range state

We report on the formation of translationally cold Cs₂ ground state molecules through photoassociation in the 1_u attractive molecular state below the 6 s _1/2 +6 p _3/2 dissociation limit. The cold molecules are obtained after spontaneous decay of photoassociated molecules in a MOT and in a dark SPOT. We also used polarized atoms, in the f =3, m f =+3Zeeman ground state. Purely asymptotic and adiabatic calculations including hyperfine interaction and rotation are in excellent agreement with observed structures. As expected, the 1_u state is actually a pure long-range state, consisting of paired atoms, uniquely linked by the first terms of the multipole expansion of the electrostatic interaction. A temperature of 20 K has been measured for the molecular cloud. Received 19 July 1999