Substituent effects on one-bond 15N?13C couplings in N,N-dimethylanilines and nitrobenzenes. Effect of steric inhibition of conjugation

The ¹J(¹⁵N¹³C) values for a series of ring-substituted N,N-dimethylaniline-¹⁵N derivatives and a series of nitrobenzene-¹⁵N derivatives were measured from the ¹³C spectra. In the nitrobenzenes, small changes in ¹J(¹⁵N¹³C) are attributed to the inductive effect of the substituents, since steric inhibition of conjugation has little effect on the magnitude of the coupling. In contrast, steric inhibition of nitrogen lone-pair delocalization in N,N-dimethylaniline derivatives markedly reduces the value of ¹J(¹⁵N¹³C). Theoretical calculations of ¹J(¹⁵N¹³C) values for the two series of compounds were made using standard INDO parameters and a ‘sum-over-states’ perturbation approach. Fair agreement between the calculated and experimental values is found.     

Search for global minimum geometries for medium sized germanium clusters: Ge12-Ge20

We have performed an unbiased search for the global minimum geometries of small-to-medium sized germanium clusters Gen(12< or =n< or =18) as well as a biased search (using seeding method) for Gen(17< or =n< or =20). We employed the basin-hopping algorithm coupled with the plane-wave pseudopotential density functional calculations. For each size, we started the unbiased search with using several structurally very different initial clusters, or we started the biased search with three different seeds. Irrespective of the initial structures of clusters we found that the obtained lowest-energy clusters of the size n=12-16 and 18 are the same. Among them, the predicted global minima of Gen(12< or =n< or =16) are identical to those reported previously [Shvartsburg et al., Phys. Rev. Lett. 83, 167 (1999)]. For n=17-20, we have identified two or three nearly isoenergetic low-lying isomers (for each size) that compete for the global minimum. Nearly all the low-lying clusters in the size range of 12< or =n< or =20 contain the tri-caped trigonal prism motif and are all prolate in geometry, in agreement with the experiment.     

On the Re-function of the A-X system of No+

The band intensity factors, and r-centroids are reported, for bands of the A-X system of NO⁺, a stable molecular ion of astrophysical and aeronomical interest. The need for further laboratory band intensity measurements, is indicated, in order to resolve the existing ambiguity of the R_e-function of the system.     

Internal Bremsstrahlung from14C and36Cl

The Internal Bremsstrahlung (IB) spectra emitted in the beta decays of¹⁴C and³⁶Cl are measured with a HPGe detector and a multichannel analyser along with a standard geometrical set up. The experimental results are compared with the corresponding theoretical distributions due to Knipp and Uhlenbeck and Bloch (KUB), Lewis and Ford, Nilsson and also due to Chang and Falkoff. The total IB yields of intensity and of energy from each of the isotopes in the investigated energy regions are also determined and compared with the corresponding theoretical values. The present results of IB from¹⁴C are found to be in excess over all the corresponding theoretical distributions throughout the investigated photon energy region from 60 keV to 130 keV. It may also be pointed out that the IB from this isotope has not been studied earlier and as such the results in this case are considered new and important. In the case of³⁶Cl the experimental results are found to be above KUB theory but corresponding closely to the theory of Chang and Falkoff, except below 150 keV where there is experimental excess over theory.