Geminal model chemistry. IV. Variational and size consistent pure spin states

We present a computationally inexpensive method that yields ground state wave functions of pure spin symmetry. The method is variational and rigorously size consistent, free from adjustable parameters, and has a favorable scaling with system size. It is based on the recently introduced partially spin restricted geminal wave functions with limited spin contamination. Computations of a bond breaking, a transition metal compound, and a symmetric hydrogen cluster confirm the properties of this method.     

Manner for Instantenious Determination of Base Impurity and Dissociation Constant of Carboxylic Acid

It is known that the commercial solvents are polluted of basic impurities as usual.     

Penta‐ and hexa‐m‐phenylcyclophosphites and their derivatives

New representatives of an original class of crown ethers—cyclopenta‐ and cyclohexaresorcinolamidophosphites—were synthesized using the molecular assemblage technique. Their thio and oxo derivatives were obtained, as well as the rhodium (I) complexes. A macrocycle containing both tri‐ and pentavalent phosphorus atoms was synthesized. ¹H and ³¹P NMR spectroscopy data suggested the higher conformational flexibility of phosphite macrocycles as compared to phosphate ones. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:129–137, 2000     

Exact Recursive Calculation of Circulant Permanents: A Band of Different Diagonals inside a Uniform Matrix

We present a finite-order system of recurrence relations for the permanent of circulant matrices containing a band of k any-value diagonals on top of a uniform matrix (for k=1,2 and 3) and the method for deriving such recurrence relations, which is based on the permanents of the matrices with defects. The proposed system of linear recurrence equations with variable coefficients provides a powerful tool for the analysis of the circulant permanents, their fast, linear-time computing; and finding their asymptotics in a large-matrix-size limit. The latter problem is an open fundamental problem. Its solution would be tremendously important for a unified analysis of a wide range of the nature’s ♯P-hard problems, including problems in the physics of many-body systems, critical phenomena, quantum computing, quantum field theory, theory of chaos, fractals, theory of graphs, number theory, combinatorics, cryptography, etc.     

Models of G time variations in diverse dimensions

A review of different cosmological models in diverse dimensions leading to a relatively small time variation in the effective gravitational constant G is presented. Among them: the 4-dimensional (4-D) general scalar-tensor model, the multidimensional vacuum model with two curved Einstein spaces, the multidimensional model with the multicomponent anisotropic “perfect fluid”, the S-brane model with scalar fields and two form fields, etc. It is shown that there exist different possible ways of explaining relatively small time variations of the effective gravitational constant G compatible with present cosmological data (e.g. acceleration): 4-dimensional scalar-tensor theories or multidimensional cosmological models with different matter sources. The experimental bounds on Ġ may be satisfied either in some restricted interval or for all allowed values of the synchronous time variable.      

The role of the bridging group in exchange coupling in dinuclear homo- and heterometallic Ni(ii) and Co(ii) complexes with oxalate, oxamidate and dithiooxamidate bridges

Six homodinuclear and two heteronuclear complexes Tp(Np)Co-C(2)O(4)-CoTp(Np) (1), Tp(Np)Co-C(2)O(4)-NiTp(Cy) (2), Tp(Cy)Ni-C(2)O(4)-NiTp(Cy) (3), Tp(Np)Co-C(2)O(2)(NH)(2)-CoTp(Np) (4), Tp(Cy)Ni-C(2)O(2)(NH)(2)-NiTp(Cy) (5), Tp(Np)Co-C(2)S(2)(NH)(2)-CoTp(Np) (6), Tp(Np)Co-C(2)S(2)(NH)(2)-NiTp(Cy) (7), Tp(Cy)Ni-C(2)S(2)(NH)(2)-NiTp(Cy) (8) (Tp(Np) = tris(3-neopentylpyrazolyl)borate, Tp(Cy) = tris(3-cyclohexylpyrazolyl)borate), were synthesized and characterized by mass spectrometry, electronic spectroscopy and X-ray crystallography. These compounds possess similar molecular structures, with the metal ions linked by bridging oxalate (1-3), oxamidate (4 and 5) or dithiooxamidate (6-8) ions. The heteronuclear nature of compounds 2 and 7 was additionally confirmed by high-resolution mass spectrometry. The magnetic properties of the Co(2+) complexes were modelled taking into account zero-field splitting of this ion, yielding D-values for Co(2+) in the range -17(1) to -50(1) cm(-1). All the metal ion pairs in compounds 1-8 are antiferromagnetically-coupled, with J values between -10.0(1) and -45.0(2) cm(-1) (via the exchange Hamiltonian ?(ex.) = -2J?(1)?(2)) and |J| increasing in the order oxalate < oxamidate < dithiooxamidate. This tendency can be attributed to greater M-S bond covalency compared to M-N or M-O bonds (M = Co(2+) and Ni(2+)). It was found that this antiferromagnetic coupling of Co(2+) and Ni(2+) ions through oxalate is more efficient for these tris(pyrazolyl)borate complexes than for similar oxalate-bridged systems with neutral aliphatic amine ligands.     

Enhancing coherent nonlinear-optical processes in nonmagnetic backward-wave materials

Novel concepts of nonlinear-optical (NLO) photonic metamaterials (MMs) are proposed. They concern with greatly enhanced coherent NLO energy exchange between ordinary and backward waves (BWs) through the frequency-conversion processes. Two different classes of materials which support BWs are considered: crystals that support optical phonons with negative group velocity and MMs with specially engineered spatial dispersion. The possibility to replace plasmonic NLO MMs enabling magnetic response at optical frequencies, which are very challenging to engineer, by the ordinary readily available crystals, are discussed. The possibility to mimic extraordinary NLO frequency-conversion propagation processes attributed to negative-index MMs (NIMs) is shown in some of such crystals, if optical phonons with negative group velocity and a proper phase-matching geometry are implemented. Here, optical phonons are used as one of the coupled counterparts instead of backward electromagnetic waves (BEMWs). The appearance of BEMWs in metaslabs made of carbon nanotubes, the possibilities and extraordinary properties of BW second harmonic generation in such MMs is another option of nonmagnetic NIMs, which is described too. Among the applications of the proposed photonic materials is the possibility of creation of a family of unique BW photonic devices such as frequency doubling metamirror and Raman amplifiers with greatly improved efficiency.     

Double and triple ionization of silver clusters by electron impact

The production of silver cluster cations Ag(n)(2+) (for several selected sizes in the range n = 39-119) and Ag(n)(3+) (for n = 58, 61, 67) by electron impact ionization of neutral precursors has been studied. The scaling of appearance energies with cluster radius follows the metallic droplet model but, curiously, with a slope which is estimated to be quite different from the literature values for single ionization, Ag(n)(+), as well as for the appearance of smaller Ag(n)(2+) ions. It is also found that as the electron energy increases, the yield of high-charge cations grows faster than that of singly-charged Ag(n)(+). This behavior is consistent with the power-law dependence of post-threshold ionization. The mechanisms involved in multiple ionization phenomena in clusters of noble metals are not yet fully understood and call for further experimental and theoretical examination.     

Lasing threshold in traps for Bose-condensation of dipolar excitons

We consider exciton recombination lasing in heterostructure traps for Bose–Einstein condensation of dipolar excitons. We show that such structures suit well for class D lasers where cavity decay strongly exceeds polarization decay. We evaluate lasing threshold taking into account specific inhomogeneous broadening of the exciton spectral line owing to Bose–Einstein condensation phenomenon under quasi-equilibrium conditions.It is found that narrowing of the exciton momentum distribution just before the condensation onset considerably lowers lasing threshold. At the same time, it is pointed out that a subsequent formation of condensate itself does not help lasing much. We conclude that it is possible to achieve lasing on polariton modes in nowadays experiments aimed on Bose–Einstein condensation of excitons.