Stereochemical applications of potential energy calculations : Part V. Conformational studies of some 1,1,2-trisubstituted ethanes by the molecular mechanics method (MM2)

The conformational distribution of some 1,1,2-trisubstituted ethanes was studied by the molecular mechanics method. An overall satisfactory correlation with experimental data is obtained, especially when these refer to experimental conditions excluding possible dimerization.     

Binding energy for inhomogeneous nuclear matter

For a spatial finite nuclear density distribution a binding energy formula is developed. A modified Thomas-Fermi method which deduces the mixed density by taking into account an anisotropic local momentum space occupation is used. This method presents the binding energy as a functional of the proton and neutron density distributions. It was possible within this framework to derive in a consistent way the energy correction terms due to density inhomogeneities. The structure of these energy correction terms is shown and an estimate is given for the adjustable parameters of this model to fit the experimental nuclear masses.     

Surface segregation and surface electronic interactions in PtCu

Photoemission and Auger electron spectroscopy on Pt_0.98Cu_0.02 show that the (110) face has over twice as much Cu surface segregation as the (111) face. The Cu 3d-derived surface “density of states” differ strikingly in peak shape and in width (by 0.5 eV). The centroids, compared with bulk Cu d states, are shifted by more than 0.3 eV towards the Fermi level. This is the first experimental correlation between surface segregation and surface bonding.     

Zum Randverhalten der Lösungen gewisser zweidimensionaler Variationsprobleme mit freien Randbedingungen

Ohne Zusammenfassung     

Four-dimensional quantum study on exothermic complex-forming reactions: Cl- + CH3Br-->ClCH3+Br-

The exothermic gas-phase bimolecular nucleophilic substitution (S(N)2) reaction Cl(-)+CH(3)Br (upsilon1',upsilon2',upsilon3')-->ClCH(3) (upsilon1,upsilon2,upsilon3)+Br- and the corresponding endothermic reverse reaction have been studied by time-independent quantum scattering calculations in hyperspherical coordinates on a coupled-cluster potential-energy surface. The dimensionality-reduced model takes four degrees of freedom into account [Cl-C and C-Br stretching modes (quantum numbers upsilon3' and upsilon3); totally symmetric modes of the methyl group, i.e., C-H stretching (upsilon1' and upsilon1) and umbrella bending vibrations (upsilon2' and upsilon2)]. Diagonalization of the Hamiltonian was performed employing the Lanczos algorithm with a variation of partial reorthogonalization. A narrow grid in the total energy was employed so that long-living resonance states could be resolved and extracted. While excitation of the reactant umbrella bending mode already leads to a considerable enhancement of the reaction probability, its combination with vibrational excitation of the broken C-Br bond, (0, 1, 1), results in a strong synergic effect that can be rationalized by the similarity with the classical transitional normal mode. Exciting the C-H stretch has a non-negligible effect on the reaction probability, while for larger translational energies this mode follows the expected spectatorlike behavior. Combination of C-Br stretch and symmetric C-H, (1,0,1), stretch does not show a cooperative effect. Contrary to the spectator mode concept, energy originally stored in the C-H stretching mode is by no means conserved, but almost completely released in other modes of the reaction products. Products are most likely formed in states with a high degree of excitation in the new C-Cl bond, while the internal modes of the methyl group are less important. Reactants with combined umbrella/C-Br stretch excitation, (0, 1, 1), may yield products with two quanta in the umbrella mode.