On the excitation of isovector dipole strength by inelastic proton scattering in the giant resonance region in light nuclei

A detailed comparison between inelastic α and p scattering in the giant resonance region of ^{24, 26}Mg, ²⁸Si and ⁴⁰Ca shows that there is no evidence for ΔT = 1, E1 excitation in the (p, p′) spectra. This is consistent with DWBA calculations using a recently obtained isovector interaction potential.     

K−p elastic scattering at 14.3 GeV/c

Results are presented of a bubble chamber experiment on K^?p elastic scattering at 14.3 GeV/c, in four-momentum transfer range 0.04 < |t| < 2.74 GeV² using an initial set of 40 000 events. The total elastic cross section is (2.96 ± 0.10) mb. The results are compared with K⁺p elastic scattering data at 13.8 GeV/c, and the effective Regge trajectory is calculated using K^?p data from 5 to 100 GeV/c.     

Assignment of molecular structures to the electrochemical reduction products of diiron compounds related to [Fe-Fe] hydrogenase: a combined experimental and density functional theory study

The reduction chemistry of (mu-bridge)[Fe(CO)3]2 [bridge = propane-1,3-dithiolate (1) and ethane-1,2-dithiolate (2)] is punctuated by the formation of distinct products, resulting in a marked difference in CO inhibition of electrocatalytic proton reduction. The products formed following reduction of 2 have been examined by a range of electrochemical, spectroelectrochemical, and spectroscopic approaches. Density functional theory has allowed assessment of the relative energies of the structures proposed for the reduction products and agreement between the calculated spectra (IR and NMR) and bond distances with the experimental spectra and EXAFS-derived structural parameters. For 1 and 2, one-electron reduction is accompanied by dimerization, but the structure, stability, and reaction with CO of the dimer is different in the two cases, and this is responsible for the different CO inhibition response for electrocatalytic proton reduction. Calculations of the alternate structures of the two-electron, one-proton reduced forms of 2 show that the isomers with terminally bound hydrides are unlikely to play a significant role in the chemistry of these species. The hydride-transfer chemistry of the 1B species is more reasonably attributed to a hydride-bridged form. The combination of experimental and computational results provides a solid foundation for the interpretation of the reduction chemistry of dithiolate-bridged diiron compounds, and this will underpin translation of the diiron subsite of the [FeFe] hydrogenase H cluster into an abiological context.     

On the structure of a proposed mixed-valent analogue of the diiron subsite of [FeFe]-hydrogenase

We show that a dinuclear assembly apparently providing the first example of a synthetic molecule exhibiting key features of the diiron subsite of [FeFe] hydrogenase, viz. CO-bridging of a coordinatively unsaturated, dithiolate-bridged mixed-valence diiron centre, is in fact a diamagnetic tetranuclear complex.     

Relative ground and excited-state pKa values of phytochromobilin in the photoactivation of phytochrome: a computational study

The conversion of the plant photoreceptor phytochrome from an inactive (Pr) to an active form (Pfr) is accomplished by a red-light induced Z --> E photoisomerization of its phytochromobilin chromophore. In recent years, the question whether the photoactivation involves a change in chromophore protonation state has been the subject of many experimental studies. Here, we have used quantum chemical methods to calculate relative ground and excited-state pKa values of the different pyrrole moieties of phytochromobilin in a protein-like environment. Assuming (based on experimental data) a Pr ZaZsZa chromophore and considering isomerizations at C15 and C5, it is found that moieties B and C are the strongest acids both in the ground state and in the bright first singlet excited state, which is rationalized in simple geometric and electronic terms. It is also shown that neither light absorption nor isomerization increases the acidity of phytochromobilin relative to the reference Pr state with all pyrrolenic nitrogens protonated. Hence, provided that the subset of chromophore geometries under investigation is biologically relevant, there appears to be no intrinsic driving force for a proton-transfer event. In a series of benchmark calculations, the performance of ab initio and time-dependent density functional theory methods for excited-state studies of phytochromobilin is evaluated in light of available experimental data.     

Why betaine crystallizes in high local Cs symmetry. An ab initio MO and DFT study of anhydrous betaine and betaine monohydrate

A theoretical study of the structure, charge distribution, rotational barrier and fundamental vibrations of anhydrous betaine (CH₃)₃NCH₂COO (trimethylglycine) was carried out and compared with available experimental data. Calculations were carried out at HF, MP2 and B3LYP levels using a 6-31+G(d,p) basis set. The calculated rotational barrier of the betaine carboxylic group is 40.5 kJ/mol at the MP4(SDQ)/6-311G(d,p)//HF/6-31+G(d,p) level of theory. The rotation of the carboxylic group changes the molecule from a highly symmetric (C _s ) conformation into a twisted conformation resulting in shortening of the molecule by about 50 pm. Natural population analysis (NPA) indicates intramolecular interaction between the carboxylic oxygen and the nearest methyl hydrogens resulting in internal hydrogen bonding. MP4(SDQ)/6-311G(d,p) single-point NPA calculations on a betaine monohydrate model taken from the X-ray geometry show an expected weakening in the internal hydrogen bond. Calculations explain why betaine preferentially crystallizes in high local C _s symmetry. Received: 24 March 1998 / Accepted: 3 September 1998 / Published online: 7 December 1998     

Mesoscale calculations of the dynamic behavior of a granular ceramic

Mesoscale calculations have been conducted in order to gain further insight into the dynamic compaction characteristics of granular ceramics. The primary goals of this work are to numerically determine the shock response of granular tungsten carbide and to assess the feasibility of using these results to construct the bulk material Hugoniot. Secondary goals include describing the averaged compaction wave behavior as well as characterizing wave front behavior such as the strain rate versus stress relationship and statistically describing the laterally induced velocity distribution. The mesoscale calculations were able to accurately reproduce the experimentally determined Hugoniot slope but under predicted the zero pressure shock speed by 12%. The averaged compaction wave demonstrated an initial transient stress followed by asymptotic behavior as a function of grain bed distance. The wave front dynamics demonstrate non-Gaussian compaction dynamics in the lateral velocity distribution and a power-law strain rate–stress relationship.