A theoretical study of configurational inversion of 1,1′-binaphthyl by molecular mechanics

The molecular mechanics method has been applied to the study of various pathways and transition states for the configurational inversion of 1,1′-binaphthyl. The preferred pathway is found to be one on the anti (“trans”) side involving one point of H?H nonbonded contact in each of two identical transition states, separated by a very shallow minimum. Very satisfactory agreement with available experimental values for the enthalpy of activation is achieved.     

Salting-in of alcohols in aqueous solutions by tetraalkylammonium bromides at the freezing temperature

The freezing-point depression of the ternary systems tetraalkylammonium bromides-t-butanol-water for the first five homologs of R₄NBr was measured. In the case of Bu₄NBr, the effect of size of the alcohol (methahol ton-butanol) was also investigated. From the corresponding freezing-point data for the binary systems the apparent salting constants were calculated. The true salting constantsk _s were obtained by extrapolation to infinite dilution. These are all very close to zero at the freezing temperature. From the corresponding thermochemical data the temperature dependence ofk _s was calculated, and above 5°C all the R₄NBr salts int-butanol; the salting-in increases with temperature and with the size of the hydrophobic cations. The scaled-particle theory is at present the only one which can account semiquantitatively for the temperature dependence of the salting-in effect. On leave of absence from Chemistry Department, The University, Sheffield S3 7HF, England To whom correspondence should be addressed.     

Comparison of diatomics-in-molecules and simple valence-bond potential surfaces for FH2

The method of diatomics-in-molecules (DIM) is applied to the FH₂ system. With spin—orbit interaction neglected, all elements of the 24 × 24 hamiltonian matrix are tabulated as analytic functions of the six diatomic fragment potential curves. It is found that neglect of off-diagonal 8 × 8 blocks in the DIM hamiltonian matrix leads to an energy expression for the ground 1 ²A′ level which is identical to the valence-bond formula used by Blais and Truhlar in dynamical studies of the F + D₂ reaction. The ²A″ excited level from DIM theory is identical to the result derived by Blais and Truhlar, without neglect of the 8 × 8 off-diagonal blocks. The DIM and simple valence-bond energies are compared numerically for noncollinear geometries.     

Orientational effects on atomic photoelectric cross sections and their relevance to photoelectron spectra from single crystals

We have examined the dependence of the photoelectric cross section from individual atomic orbitals and from groups of orbitals adapted to crystal symmetries in order to ascertain the relevance of this effect to the photoelectron spectra arising from single crystals.     

A new approach to intermolecular forces in non-bonding regions

A new method to compute intermolecular energies in non-bonding regions is presented. It is based on the assumption that in such regions molecules can be reviewed as the sum of distorted, possibly overlapping, and electron exchanging atoms. The intermolecular energy change at a given distance is due to the sum of the atomic energy changes caused by these distortions. The energy change of any particular atom is computed in a Hartree—Fock model in which the effect of the other atom is represented by an effective potential. This potential in turn is computed from a calculation at a slightly larger intermolecular distance of the potential seen by an external electron in the field of the “other” atom. This potential computed in the RPA approximation and involves the distorted Hartree—Fock orbitals of the other atom (computed in a similar manner to the above) and the RPA response function of the other distorted atom.     

Non-empirical calculations on the rydberg states of ethylene

Different methods for representing the upper orbitals in Rydberg transitions are tested by means of a series of ab initio SCF and CI calculations for ethylene and various properties for such diffuse united-atom species are reported. Calculated transition energies indicates the maximum separation between individual components of the (π,3d) Rydberg species to be in the 0.1-0.2 range, with similarly small energy separations being obtained for the corresponding (π, 3p) states     

Styrene emulsion polymerization: Particle-size distributions

Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments.     

Benzothiazolium derivatives. III. Nucleophilic substitution reactions of benzothiazolium salts

The reactions of 2,3-dihydrothiazolo[2,3-b]benzothiazolium bromide 1 (A^? ?Br^?) with certain nucleophilic reagents have been performed for the purpose of ascertaining the reaction pathways and identifying the group that is displaced from the central carbon atom of the dithiocarbamate system. The nature of complex salt-like intermediates formed initially from 1 (A^? ?Br^?) has been studied and confirmed. For comparison, a number of nucleophilic substitution reactions of 2-methylthio-3-methylbenzothiazolium iodide 17 and 2-dimethylamino-3-methylbenzothiazolium perchlorate 18 have been examined.     

Obtaining partial widths from siegert wavefunctions

It is shown that a simple expression for the partial widths in a multichannel decay problem can be readily obtained from a Siegert wavefunction.