Submanifolds of Weyl Flat Manifolds

 We consider compact Weyl submanifolds of Weyl flat manifolds with special attention on compact Einstein-Weyl hypersurfaces. In particular, in the last part of the paper, we study Weyl submanifolds of special noncompact manifolds, called PC-manifolds. Received July 16, 2001; in revised form February 6, 2002 Published online August 9, 2002     

Complex formation equilibria of some β-amino-alcohols with lead(II) and cadmium(II) in aqueous solution

A study of complex formation equilibria of some β-amino-alcohols with lead(II) and cadmium(II) ions at 25°C and in 0.5 M KNO₃ is reported. The amino-alcohols considered are 2-amino-1-propanol, 2-amino-1-butanol, 2-amino-1-pentanol and 2-amino-1,3-propanediol. sec-Buthylamine and 2-amino-1-methoxy-propane have been also considered for comparison. The results are discussed in terms of ligand structure, paying attention to the number of hydroxyl groups and to the length of the alkyl residual. A weak contribution of the alcoholic oxygen in the coordination of cadmium(II) and the presence of a mixed hydroxyl species in lead(II) containing systems are hypothesized.     

Gas-phase chemistry of ionized and protonated GeF4: a joint experimental and theoretical study

The gas-phase ion chemistry of GeF(4) and of its mixtures with water, ammonia and hydrocarbons was investigated by ion trap mass spectrometry (ITMS) and ab initio calculations. Under ITMS conditions, the only fragment detected from ionized GeF(4) is GeF(3)(+). This cation is a strong Lewis acid, able to react with H(2)O, NH(3) and the unsaturated C(2)H(2), C(2)H(4) and C(6)H(6) by addition-HF elimination reactions to form F(2)Ge(XH)(+), FGe(XH)(2)(+), Ge(XH)(3)(+) (X = OH or NH(2)), F(2)GeC(2)H(+), F(2)GeC(2)H(3)(+) and F(2)GeC(6)H(5)(+). The structure, stability and thermochemistry of these products and the mechanistic aspects of the exemplary reactions of GeF(3)(+) with H(2)O, NH(3) and C(6)H(6) were investigated by MP2 and coupled cluster calculations. The experimental proton affinity (PA) and gas basicity (GB) of GeF(4) were estimated as 121.5 ± 6.0 and 117.1 ± 6.0 kcal mol(-1), respectively, and GeF(4)H(+) was theoretically characterized as an ion-dipole complex between GeF(3)(+) and HF. Consistently, it reacts with simple inorganic and organic molecules to form GeF(3)(+)-L complexes (L = H(2)O, NH(3), C(2)H(2), C(2)H(4), C(6)H(6), CO(2), SO(2) and GeF(4)). The theoretical investigation of the stability of these ions with respect to GeF(3)(+) and L disclosed nearly linear correlations between their dissociation enthalpies and free energies and the PA and GB of L. Comparing the behavior of GeF(3)(+) with the previously investigated CF(3)(+) and SiF(3)(+) revealed a periodically reversed order of reactivity CF(3)(+) < GeF(3)(+) < SiF(3)(+). This parallels the order of the Lewis acidities of the three cations.     

Ru2+ complexes comprising terpyridine ligands appended with terthiophene chromophores: energy transfer and energy reservoir effect

Two Ru(2+) complexes containing terpyridine ligands appended with terthiophene units connected by a methyleneoxy or an alkynyl bridge show very different luminescent behaviours: the former is non-luminescent at 298 K owing to a photoinduced energy transfer process to the terthiophene moiety, while the latter exhibits an extraordinary long excited state lifetime because of an energy reservoir effect.     

Charge-assisted hydrogen bond-directed self-assembly of an amphiphilic zwitterionic quinonemonoimine at the liquid-solid interface

Charge-assisted hydrogen bond-directed self-assembly of a zwitterionic quinonemonoimine was investigated at the liquid/solid interface using scanning tunnelling microscopy. Factors governing morphology, chirality and multilayer formation are discussed, presenting an important foundation for understanding the properties of a large family of related molecules with interesting potential in supramolecular design.     

Mechanism of the initial stages of nitrogen-doped single-walled carbon nanotube growth

We have studied the mechanism of the initial stages of nitrogen-doped single-walled carbon nanotube growth illustrated for the case of a floating catalyst chemical vapor deposition system, which uses carbon monoxide (CO) and ammonia (NH(3)) as precursors and iron as a catalyst. We performed first-principles electronic-structure calculations, fully incorporating the effects of spin polarization and magnetic moments, to investigate the bonding and chemistry of CO, NH(3), and their fragments on a model Fe(55) icosahedral cluster. A possible dissociation path for NH(3) to atomic nitrogen and hydrogen was identified, with a reaction barrier consistent with an experimentally determined value we measured by tandem infrared and mass spectrometry. Both C-C and C-N bond formation reactions were found to be barrierless and exothermic, while a parasitic reaction of HCN formation had a barrier of over 1 eV.     

Are electrophilicity and electrofugality related concepts? A density functional theory study

It is proposed that the electrofugality of a fragment within a molecule is determined by its group nucleophilicity. The variation of electrofugality should be tightly related to the electron releasing ability of the substituent attached to the electrofuge moiety. This contribution closes the set of relationships between philicity and fugality quantities: while nucleofugality appears related to the group electrophilicity of the leaving group, electrofugality is related to the group nucleophilicity of the permanent group.