A comparative study of bent-bond vs. Walsh model in strained systems. Bicyclo(1.1.0)butane

Bent bond and Walsh models for the electronic structure of the highly strained bicyclo(1.1.0)butane were critically examined and compared with the available PE spectrum. It is found that the bent bond scheme is by far more superior to the widely used Walsh semilocalized molecular orbitals. Hence the local hybrid orbitals provide a useful aid in assigning and interpreting of PE spectra. Present results lend support to the hybrid model in bicyclo(1.1.0)butane proposed by Schulman.     

Interpretation of Brønsted acidity by triadic paradigm: a G3 study of mineral acids

Deprotonation enthalpies and the gas-phase acidities of 24 inorganic acids are calculated by using composite G3 and G2 methodologies. The computed values are in very good accordance with available measured data. It is found that the experimental DeltaH(acid) values of the FSO(3)H and CF(3)SO(3)H are too high by some 6 and 7 kcal mol(-1), respectively. Furthermore, a new DeltaH(acid) value for HClO(4) of 300 kcal mol(-1) is recommended and suggested as a threshold of superacidicity in the gas phase. The calculated deprotonation enthalpies are interpreted by employing the trichotomy paradigm. Taking into account that the deprotonation enthalpy is a measure of acidity, it can be safely stated that the pronounced acidities of mineral acids are to a very large extent determined by Koopmans' term with very few exceptions, one of them being H(2)S. To put it in another way, acidities are predominantly a consequence of the ability of the conjugate bases to accommodate the excess electron charge, since Koopmans' term in trichotomy analysis is related to conjugate base anion. The final state is decisive in particular for superacids like ClSO(3)H, CF(3)SO(3)H, HClO(4), HBF(4), HPF(6), HAlCl(4), and HAlBr(4). However, in the latter two molecules the bond dissociation energy of the halogen-H bond substantially contributes to their high acidity too. Therefore, acidity of these two most powerful superacids studied here is determined by cooperative influence of both initial and final state effects. It should be emphasized that acidity of hydrogen halides HCl and HBr is a result of concerted action of all three terms included in triadic analysis. A byproduct of the triadic analysis are the first adiabatic ionization energies of the anionic conjugate bases. They are in fair to good agreement with the experimental data, which are unfortunately sparse. A fairly good qualitative correlation is found between the gas-phase deprotonation enthalpies of six mineral O-H acids and available Hammett-Taft sigma(p)- constants of the corresponding substituent groups.     

Acidities of azoles in the gas phase and in DMSO: an ab initio and DFT study

Acidity of azoles, a very important family of biological molecules with useful pharmacological applications, is examined in the gas phase and in DMSO. The gas phase proton affinities of the corresponding conjugate bases are calculated by the G3 computational scheme and used as a measure of acidity. A good accordance with available experimental data is obtained. It is confirmed that acidity increases with the number of nitrogen atoms in the five-membered ring. The calculated deprotonation energies are interpreted by the triadic formula. It turns out that acidity of azoles is a result of the final state effect and the relaxation energy contribution. It is shown, by using NICS(1) values, that azoles are aromatic compounds and that their aromatic character increases with the number of N atoms. It is also found that aromaticity slightly increases upon deprotonation. Acidity of azoles in DMSO is considered using the isodensity polarized continuum model (IPCM) at the DFT-B3LYP level. A good agreement with accessible experimental results is obtained again. In other cases pK_a values are theoretically predicted and it was found that pentaazole is the most acidic compound with pK_a?=?2. A very good linear relation between theoretical pK_a values and calculated proton affinities of conjugate bases is obtained implying that the trend of changes in the gas phase and in the DMSO solutions is the same.     

Finite nonabelian p-groups all of whose nonabelian maximal subgroups are either metacyclic or minimal nonabelian

We give here a complete classification of the title groups (Theorem A).     

A block algorithm for computing antitriangular factorizations of symmetric matrices

Any symmetric matrix can be reduced to antitriangular form in finitely many steps by orthogonal similarity transformations. This form reveals the inertia of the matrix and has found applications in, e.g., model predictive control and constraint preconditioning. Originally proposed by Mastronardi and Van Dooren, the existing algorithm for performing the reduction to antitriangular form is primarily based on Householder reflectors and Givens rotations. The poor memory access pattern of these operations implies that the performance of the algorithm is bound by the memory bandwidth. In this work, we develop a block algorithm that performs all operations almost entirely in terms of level 3 BLAS operations, which feature a more favorable memory access pattern and lead to better performance. These performance gains are confirmed by numerical experiments that cover a wide range of different inertia.     

Gas-phase dissociation reactions of protonated saxitoxin and neosaxitoxin

The aim of this study was to investigate the behavior of the protonated paralytic shellfish poisons saxitoxin (STX) and neosaxitoxin (NEO) in the gas-phase after ion activation using different tandem mass spectrometry techniques. STX and NEO belong to a group of neurotoxins produced by several strains of marine dinoflagellates. Their chemical structures are based on a tetrahydropurine skeleton to which a 5-membered ring is fused. STX and NEO only vary in their substituent at N-1, with STX carrying hydrogen and NEO having a hydroxyl group at this position. The collision-induced dissociation (CID) spectra exhibited an unusually rich variety and abundance of species due to the large number of functional groups within the small skeletal structures. Starting with triple-quadrupole CID spectra as templates, linked ion-trap MSn data were added to provide tentative dissociation schemes. Subsequent high-resolution FTICR experiments gave exact mass data for product ions formed via infrared multiphoton dissociation (IRMPD) from which elemental formulas were derived. Calculations of proton affinities of STX and NEO suggested that protonation took place at the guanidinium group in the pyrimidine ring for both molecules. Most of the observed parallel and consecutive fragmentations could be rationalized through neutral losses of H2O, NH3, CO, CO2, CH2O and different isocyanate, ketenimine and diimine species, many of which were similar for STX and NEO. Several exceptions, however, were noted and differences could be readily correlated with reactions involving NEO's additional hydroxyl group. A few interesting variations between CID and IRMPD spectra are also highlighted in this paper.     

A correlation of the limiting viscosity number, molecular mass and composition of statistical linear styrene-methyl methacrylate copolymers

Statistical copolymers of styrene and methyl methacrylate of different compositions were synthesized by the radical solution copolymerization in a batch isothermal reactor. Copolymers were characterized by the size exclusion chromatography (SEC), elemental analysis and dilute solution viscometry. Experimental limiting viscosity numbers were described by the Mark-Houwink-Kuhn-Sakurada correlation as the function of the molar mass and by the Mendelson correlation as the function of both the molar mass and copolymer composition. A new correlation of the intrinsic viscosity number, molar mass and composition was developed, based on semiempirical considerations. The correlation takes into consideration all the effects which affect the dimensions of random linear copolymer coils in solvents. The new equation was found to be superior to the Mendelson’s one in correlating the experimentally obtained intrinsic viscosities.     

Finite 2-groups all of whose nonabelian subgroups are generated with involutions

In this note we determine finite nonabelian 2-groups G all of whose nonabelian subgroups are generated by involutions and show that such groups must be quasi-dihedral. This solves the problem Nr. 1595 for p = 2 in [1].     

Finite quaternion-free 2-groups

We present an elementary proof of the classification theorem for finite nonmodular quaternion-free 2-groups. This proof does not involve the structure theory of powerful 2-groups. Such a new proof is also necessary, since there are several gaps in the original proof given in [5].