Links in a thickened surface

For a given two-dimensional surface μ, we studi invariants for oriented links in μ×[0,1] which generalize the two-variable HOMFLY polynomials when μ is the 2-disk. These invariants are connected to multiparameter quantum groups whose special properties are discussed. Si studiano gli invarianti dei nodi in spazi del tipo μ×[0,1], dove μ è una superficie. Questi invarianti generalizzano gli invarianti di HOMFLY.

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(Conferenza tenuta dal Prof. P. Cotta-Ramusino il 16 maggio 1991)     

2D Ising Model with Layers of Quenched Spins

The model considered is a d=2 disordered Ising system on a square lattice with nearest neighbor interaction. The disorder is induced by layers (rows) of spins, randomly located, which are frozen in an antiferromagnetic order. It is assumed that all the vertical couplings take the same positive value J _v, while all the horizontal couplings take the same positive value J _h. The model can be exactly solved and the free energy is given as a simple explicit expression. The zero-temperature entropy can be positive because of the frustration due to the competition between antiferromagnetic alignment induced by the quenched layers and ferromagnetic alignment due to the positive couplings. No phase transition is found at finite temperature if the layers of frozen spins are independently distributed, while for correlated disorder one finds a low-temperature phase with some glassy properties.     

The crystal structure of tris(acetonitrile)nitrosylbis(triphenylphosphine)iridium(III) dihexafluorophosphate. An unusual iridium nitrosyl hexacoordinate complex

Summary The structure of [Ir(NCMe)₃(NO)(PPh₃)₂][PF₆]₂ has been ] determined by x-ray methods. Crystals are orthorhombic, space groupPca 2₁ , witha = 21.753(14),b = 11.678(10),c = 18.474(12) Å and Z = 4. The structure has been solved from diffractometer data and refined by full-matrix leastsquares to R = 0.076 for 2776 observed reflections. The cation is a hexacoordinate and not a pentacoordinate species as expected. The extra acetonitrile molecule,trans to the nitrosyl ligand, is much more weakly bound to the metal atom [Ir-N 2.360(26) against 1.965(20) and 1.912(14) Å for the other two acetonitriles]. The nitrosyl is bent [Ir-N-O 111(1)° Å] and acts as the formally one-electron donor NO^–.     

Polar substituent effects in the bicyclo[1.1.1]pentane ring system: acidities of 3-substituted bicyclo[1.1.1]pentane-1-carboxylic acids

Experimental gas-phase acidities are reported for a series of 3-substituted (X) bicyclo [1.1.1]pent-1-yl carboxylic acids (1, Y = COOH). A comparison with available calculated data (MP2/6-311++G**// B3LYP/6-311+G**) reveals good agreement. The relative substituent effects are shown to be adequately described by a much lower level of theory (B3LYP/6-31+G*). Various correlations are presented which clearly point to polar field effects as being the origin of the relative acidities.     

Excited state dynamics with the direct trajectory surface hopping method: azobenzene and its derivatives as a case study

We review the recent studies of the photoisomerization dynamics of azobenzene and its derivatives by surface hopping simulations based on semiempirical potential energy surfaces. We examine the ability of semiclassical methods to predict the excited state dynamics and to reproduce transient spectroscopic signals that constitute the most direct experimental evidence in this field. We show that the available simulation methods yield a deep insight into the mechanism of photochemical reactions and excited state decay, and a fairly good quantitative agreement with experimental findings. Probably the most important technical improvements we can envisage concern the surface hopping algorithm and the usage of ab initio data in the simulation of transient spectra. Concerning azobenzene, our results show that the isomerization mechanism is torsion of the N=N double bond, both by n → π* and by π → π* excitation. The influence of the solvent and the findings of some recent femtochemistry experiments deserve further work to be fully interpreted.     

Synthesis and N.m.r. studies of bis-trisubstituted phosphine platinum(o) and palladium(o) complexes with push-pull olefins

Summary Platinum(0) and palladium(0) complexes of the type: P₂M(R₁R₂C=CR₃R₄) (P=trisubstituted phosphine; R₁, R₂, R₃ and R₄ are different groups having electron acceptor or electron donor properties; M=Pt or Pd) with so called pushpull olefins, have been prepared and characterized. In some cases unusual patterns in the n.m.r. spectra of olefinic protons were observed. The spectra were analyzed by computer simulation and general rules for ABMX patterns for this type of complexes are given.     

Experimental and theoretical study of the interaction of CO2 with alpha-Al2O3

Density functional molecular cluster calculations are combined with X-ray photoelectron spectroscopy (XPS), quadrupolar mass spectrometry (QMS), and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy to investigate the interaction of CO2 with alpha-Al2O3 and partially reduced alpha-Al2O3. The electronic structure of the stoichiometric and partially reduced substrate, adsorbate geometries, chemisorption enthalpies, and adsorbate vibrational parameters are computed and discussed. Theoretical results agree quite well with experimental data and previous theoretical investigations. As far as the adsorbate-substrate interaction is concerned, the results of our calculations indicate that CO2 forms bidentate-chelating carbonate species. The bonding scheme of this surface complex implies a significant substrate-->adsorbate transfer of charge (from the occupied dangling bond of a surface Lewis base site into one component of the CO2 2 pi u LUMO) assisted by a definitely weaker adsorbate-->substrate donation (from one component of the CO2 1 pi g HOMO into an empty dangling bond of a surface Lewis acid site). Our estimate of the chemisorption enthalpy (-15 kcal/mol) agrees quantitatively with calorimetric data reported for CO2 adsorbed on high surface area alpha-alumina (-16.0 kcal/mol). [Mao, C.-F.; Vannice, M. A. Appl. Catal. A 1994, 111, 151.] According to XPS and QMS outcomes, theoretical results predict that the interaction of CO2 with partially reduced alpha-Al2O3 gives rise to the reduction of the adsorbate to CO and to the concomitant substrate reoxidation.