Single-Proton states of159Ho studied with the (p,α) reaction spectroscopic evidence for the unusual coriolis strengths in159, 161, 163Ho nuclei

The proton-hole character of states in¹⁵⁹Ho has been studied using the^{162, 164}Er(p, α)^{159, 161}Ho reactions with 17 MeV protons. The shapes of angular distributions measured for both nuclei were compared, with good agreement in most cases, to tritoncluster-transfer DWBA calculations. The deviations obtained and the experimental normalization factors deduced for the¹⁶⁴Er(p, α)¹⁶¹Ho reaction by comparisons to (t, α) cross sections indicate a need for a revised treatment of the mechanism of the (p, α) reaction on deformed nuclei. By comparisons to the well-known states in¹⁶¹Ho, nuclear structure factors were obtained for many levels in¹⁵⁹Ho. The Nilsson assignments for the 3/2⁺[411], 5/2^?[532] and 5/2⁺[413] bands were confirmed and the lowest rotational members of these bands were established. The anomalous strengths of the strongly mixed positive parity states in^{159, 161, 163}Ho are discussed in the frame-work of the Nilsson model with the pairing and effective Coriolis strengths included. The Coriolis strengths giving best fits to excitation energies also improve the agreement of theory with the experimental nuclear structure factors. Rotational spacings of the 5/2⁺[413] and especially those of the 5/2^?[532] bands in^{159, 161, 163}Ho show mixmg effects unexplainable by the present calculations.     

High spin shell model excitations in149Gd

The high spin level structure of the three-neutron nucleus¹⁴⁹Gd has been investigated by in-beamγ-ray and electron spectroscopy with (α, xn) reactions. The observed levels are characterized as members of the shell model multipletsνf ₇ ^2/3 ,νh _9/2 f ₇ ^2/2 ,νf ₇ ^2/3 ×3^?,νh _9/2 f ₇ ^2/2 ×3^?, and tentativelyνf ₇ ^2/3 ×(3^?)². The energies of theν f ₇ ^2/3 states agree only moderately with those calculated using empirical two-nucleon interactions taken from¹⁴⁸Gd, which indicates the importance of long range contributions already atN=85.     

Additions to bicyclic olefins—X: Stereochemistry of the oxymercuration-demercuration of cis-bicyclo[3.3.0]oct-2-ene,endo-trimethylene-norborn-8-ene and related olefins

The stereochemistry of the oxymercuration-demercurarion (OM-DM) of olefins related to the cis-bicyclo(3.3.0]octane and endo-2,3-trimethylenenorboniane structures was determined. In the case of cis-bicyclo(3.3.0]oct-2-ene, hydration occurs preferentially at the less hindered 3-position, with little preference shown for exo vs endo. The more hindered 2-product shows a 11:1 preference for the exo-product. The presence of Me groups at positions 2- or 3-, results in the formation of the tertiary alcohols with approximately a 4:1 favoring of the exo-isomer. (The oxymercuration intermediate exhibits a rapid equilibration with time. Consequently, the 4:1 ratios may not represent the true limit for the isomer distribution in the initial kinetic product.) Similarly, 2-methylenebicyclo[3.3.0]octane reveals an 8:1 preferential formation of the exo-alcohol. In the case of endo-trimethylene-norborn-8-ene, the oxymercuration stage is extraordinarily slow and the results do not fit this pattern. Possibly the very slow oxymercuration stage permits equilibration of the initial reaction product. On the other hand, the reaction is fast with 8-methylene-endo-trimethylenenorbornane and the product is 100% of the tertiary exo-alcohol. The same behavior is observed for 2-methylenenorbornane. Surprisingly, 2-methylene-endo-trimethy-lenenorbornane fails to undergo oxymercuration. Consequently, both endo-trimethylenenorborn-8-ene and 2-methylene-endo-trimethylenenorbornane exhibit an exceptional inertness toward oxymercuration, presumably related to the highly rigid U-shaped structure of the parent system.     

Phosphoric acid catalyzed enantioselective transfer hydrogenation of imines: a density functional theory study of reaction mechanism and the origins of enantioselectivity

The phosphoric acid catalyzed reaction of 1,4‐dihydropyridines with N‐arylimines has been investigated by using density functional theory. We first considered the reaction of acetophenone PMP‐imine (PMP=p‐methoxyphenyl) with the dimethyl Hantzsch ester catalyzed by diphenyl phosphate. Our study showed that, in agreement with what has previously been postulated for other reactions, diphenyl phosphate acts as a Lewis base/Brønsted acid bifunctional catalyst in this transformation, simultaneously activating both reaction partners. The calculations also showed that the hydride transfer transition states for the E and Z isomers of the iminium ion have comparable energies. This observation turned out to be crucial to the understanding of the enantioselectivity of the process. Our results indicate that when using a chiral 3,3′‐disubstituted biaryl phosphoric acid, hydride transfer to the Re face of the (Z)‐iminium is energetically more favorable and is responsible for the enantioselectivity, whereas the corresponding transition states for nucleophilic attack on the two faces of the (E)‐iminium are virtually degenerate. Moreover, model calculations predict the reversal in enantioselectivity observed in the hydrogenation of 2‐arylquinolines, which during the catalytic cycle are converted into (E)‐iminium ions that lack the flexibility of those derived from acyclic N‐arylimines. In this respect, the conformational rigidity of the dihydroquinolinium cation imposes an unfavorable binding geometry on the transition state for hydride transfer on the Re face and is therefore responsible for the high enantioselectivity.     

Effect of three-body forces on the lattice dynamics of noble metals

A simple method to generate an effective electron-ion interaction pseudopotential from the energy wave number characteristic obtained by first principles calculations has been suggested. This effective potential has been used, in third order perturbation, to study the effect of three-body forces on the lattice dynamics of noble metals. It is found that three-body forces, in these metals, do play an important role. The inclusion of such three-body forces appreciably improves the agreement between the experimental and theoretical phonon dispersion curves.     

Unrestricted symmetry-projected Hartree-Fock-Bogoliubov calculations for some PF-shell nuclei

Total binding energies and yrast energy spectra of three selected 1p0f–nuclei have been calculated using an unrestricted Hartree–Fock–Bogoliubov approach with symmetry–projection before the variation. The full 1p0f–shell has been used as single–particle basis and the semi–empirical FPD6 interaction as effective Hamiltonian. The results are compared to those of truncated shell–model calculations performed with the OXBASH code. In the middle of the 1p0f–shell the variational method yields energy gains up to 4.5 MeV and thus proves to be far superior than the conventional truncation methods at least if in the latter only up to about 13000 configurations for each spin–isospin combination are admitted. Received: 15 September 1999