Deactivation of vibrationally excited hydrogen fluoride (v=2 and v=1) by atomic fluorine

Measurements have been made which provide information concerning the rate of energy transfer between vibrationally excited HF and atomic fluorine. It was found that HF (v = 1) deactivates about seven times slower than was determined in previous experiments. The deactivation rate constant for HF (v = 2) is about six times larger than for HF (v = 1).     

The determination of chlorine in organic materials by combustion and microcoulometry

A combustion apparatus capable of burning both solid and liquid samples is described. The samples were vaporized in helium and then burned in humid oxygen. Oxygen was then used to burn non-volatile residues within the vaporization chamber. The use of cheap, disposable vaporization chambers eliminated carryover from one analysis to the next. The application of this instrument to the determination of organochlorine-containing samples is described. The moist effluent hydrogen chloride from the combustion was condensed and the chloride content was determined by microcoulometry. Pure solutions of high-boiling inorganic chlorides did not evolve chloride but the addition of an amino acid resulted in evolution of all of the chloride present.     

Entanglement formation and violation of Bell's inequality with a semiconductor single photon source

We report the generation of polarization-entangled photons, using a quantum dot single photon source, linear optics, and photodetectors. Two photons created independently are observed to violate Bell's inequality. The density matrix describing the polarization state of the postselected photon pairs is reconstructed and agrees well with a simple model predicting the quality of entanglement from the known parameters of the single photon source. Our scheme provides a method to create no more than one entangled photon pair per cycle after postselection, a feature useful to enhance quantum cryptography protocols based on shared entanglement.     

Controlling the spontaneous emission rate of single quantum dots in a two-dimensional photonic crystal

We observe large spontaneous emission rate modification of individual InAs quantum dots (QDs) in a 2D photonic crystal with a modified, high-Q single-defect cavity. Compared to QDs in a bulk semiconductor, QDs that are resonant with the cavity show an emission rate increase of up to a factor of 8. In contrast, off-resonant QDs indicate up to fivefold rate quenching as the local density of optical states is diminished in the photonic crystal. In both cases, we demonstrate photon antibunching, showing that the structure represents an on-demand single photon source with a pulse duration from 210 ps to 8 ns. We explain the suppression of QD emission rate using finite difference time domain simulations and find good agreement with experiment.     

Spectroscopic studies of the effect of ligand donor strength on the Fe-NO bond intradiol dioxygenases

The geometric and electronic structure of NO bound to reduced protocatechuate 3,4-dioxygenase and its substrate (3,4-dihydroxybenzoate, PCA) complex have been examined by X-ray absorption (XAS), UV-vis absorption (Abs), magnetic circular dichroism (MCD), and variable temperature variable field (VTVH) MCD spectroscopies. The results are compared to those previously published on model complexes described as [FeNO]7 systems in which an S = 5/2 ferric center is antiferromagnetically coupled to an S = 1 NO-. XAS pre-edge analysis indicates that the Fe-NO units in FeIIIPCD[NO-] and FeIIIPCD[PCA,NO-] lack the greatly increased pre-edge intensity representative of most [FeNO]7 model sites. Furthermore, from extended X-ray absorption fine structure (EXAFS) analysis, the FeIIIPCD[NO-] and FeIIIPCD[PCA,NO-] active sites are shown to have an Fe-NO distance of at least 1.91 A, approximately 0.2 A greater than those found in the model complexes. The weakened Fe-NO bond is consistent with the overall lengthening of the bond lengths and the fact that VTVH MCD data show that NO(-)-->FeIII CT transitions are no longer polarized along the z-axis of the zero-field splitting tensor. The weaker Fe-NO bond derives from the strong donor interaction of the endogenous phenolate and substrate catecholate ligands, which is observed from the increased intensity in the CT region relative to that of [FeNO]7 model complexes, and from the shift in XAS edge position to lower energy. As NO is an analogue of O2, the effect of endogenous ligand donor strength on the Fe-NO bond has important implications with respect to O2 activation by non-heme iron enzymes.     

Reactive glass and vegetation patterns

The formation of vegetation patterns in the arid and the semiarid climatic zones is studied. Threshold for the biomass of the perennial flora is shown to be a relevant factor, leading to a frozen disordered pattern in the arid zone. In this "glassy" state, vegetation appears as singular plant spots separated by irregular distances, and an indirect repulsive interaction among shrubs is induced by the competition for water. At higher precipitation rates, the diminishing of hydrological losses in the presence of flora becomes important and yields spatial attraction and clustering of biomass. Turing patterns with characteristic length scale emerge from the disordered structure due to this positive-feedback instability.     

Rapid-freeze-quench magnetic circular dichroism of intermediate X in ribonucleotide reductase: new structural insight

To elucidate the electronic structure of intermediate X in the oxygen activation reaction of the R2 subunit of ribonucleotide reductase, a protocol has been developed to perform magnetic circular dichroism (MCD) on a rapid-freeze-quench, strain free optical sample. RFQ-MCD data have been collected on intermediate X in the double mutant of R2, Y122/Y356F. While X has been reported to exhibit a broad absorption band at 365 nm, there are at least 10 electronic transitions observed at low-temperature MCD. From C0/D0 ratios, the transitions of X can be divided into three regions: 16 000-22 000 cm-1 region involving spin-allowed ligand field transitions of the Fe(IV), 23 000-24 000 cm-1 region of spin-forbidden, spin-flip transitions on the Fe(IV), and the charge transfer (CT) region from 26 000 to 32 000 cm-1. The C0/D0 ratios from d --> d and CT transitions strongly support significant Fe(IV) character coupled into the paramagnetic center. Ligand field (spin-allowed d --> d region) analysis allows the bis-mu-oxo and mu-oxo plus other monoanionic bridge possibilities for the structure of intermediate X to be distinguished, providing new insight into the molecular mechanism of the cluster formation in R2.     

L-edge X-ray absorption spectroscopy of non-heme iron sites: experimental determination of differential orbital covalency

X-ray absorption spectroscopy has been utilized to obtain the L-edge multiplet spectra for a series of non-heme ferric and ferrous complexes. Using these data, a methodology for determining the total covalency and the differential orbital covalency (DOC), that is, differences in covalency in the different symmetry sets of the d orbitals, has been developed. The integrated L-edge intensity is proportional to the number of one-electron transition pathways to the unoccupied molecular orbitals as well as to the covalency of the iron site, which reduces the total L-edge intensity and redistributes intensity, producing shake-up satellites. Furthermore, differential orbital covalency leads to differences in intensity for the different symmetry sets of orbitals and, thus, further modifies the experimental spectra. The ligand field multiplet model commonly used to simulate L-edge spectra does not adequately reproduce the spectral features, especially the charge transfer satellites. The inclusion of charge transfer states with differences in covalency gives excellent fits to the data and experimental estimates of the different contributions of charge transfer shake-up pathways to the t(2g) and e(g) symmetry orbitals. The resulting experimentally determined DOC is compared to values calculated from density functional theory and used to understand chemical trends in high- and low-spin ferrous and ferric complexes with different covalent environments. The utility of this method toward problems in bioinorganic chemistry is discussed.     

Toward a Characterization of Conway's Group Co3

In this paper, Conway's group, Co₃, is characterized among simplegroups of even type with e(G) = 3, by a restriction on the p-localstructure for some odd prime p for which m_2,p(G) = 3. 2000 MathematicsSubject Classification 20D05.