Generator Coordinate Truncations

We investigate the accuracy of several schemes to calculate ground-state correlation energies using the generator coordinate technique. Our test-bed for the study is the $sd$ interacting boson model, equivalent to a 6-level Lipkin-type model. We find that the simplified projection of a triaxial generator coordinate state using the $S_3$ subgroup of the rotation group is not very accurate in the parameter space of the Hamiltonian of interest. On the other hand, a full rotational projection of an axial generator coordinate state gives remarkable accuracy. We also discuss the validity of the simplified treatment using the extended Gaussian overlap approximation (top-GOA), and show that it works reasonably well when the number of boson is four or larger.Comment: 19 pages, 6 eps figure

Electrospray Mass Spectrometric Detection of Products and Short-Lived Intermediates in Aqueous Aerosol Microdroplets Exposed to a Reactive Gas

The intermediates ISO_3^- (m/z = 207) and IS2O3- (m/z = 239) generated in aqueous (NaI/Na_2S2O_3) microdroplets traversing dilute O_3 gas plumes are detected via online electrospray mass spectrometry within ∼1 ms, and their stabilities gauged by collisionally induced dissociation. The simultaneous detection of anionic reactants and the S_2O_6^(2-), HSO_4^-, IO_3^-, and I_3^- products as a function of experimental conditions provides evidence of genuinely interfacial reaction kinetics. Although O_3(aq) reacts about 3 times faster with I- than with S_2O_3^(2-) in bulk solution, only S_2O_3^(2-) is significantly depleted in the interfacial layers of [I^-]/[S_2O_3^(2-)] = 10 microdroplets below [O_3(g)] ∼ 50 ppm

Anomalous phonon behavior in the high temperature shape memory alloy: TiPd:Cr

Ti50 Pd50-xCrx is a high temperature shape memory alloy with a martensitic transformation temperature strongly dependent on the Cr composition. Prior to the transformation a premartensitic phase is present with an incommensurate modulated cubic lattice with wave vector of q0=(0.22, 0.22, 0). The temperature dependence of the diffuse scattering in the cubic phase is measured as a function temperature for x=6.5, 8.5, and 10 at. %. The lattice dynamics has been studied and reveals anomalous temperature and q-dependence of the [110]-TA2 transverse phonon branch. The phonon linewidth is broad over the entire Brillouin zone and increases with decreasing temperature, contrary to the behavior expected for anharmonicity. No anomaly is observed at q0. The results are compared with first principles calculation of the phonon structure.Comment: 26 pages, 11 figure

Mechanisms of Acido-Tolerance and Characteristics of Photosystems in an Acidophilic and Thermophilic Red Alga, Cyanidium Caldarium

In this chapter, we describe the mechanisms of acido-tolerance in an acidophilic- and thermophilic red alga, Cyanidium caldarium. In spite of the extremely acidic environments it inhabits, the intracellular pH of Cyanidium cells is kept neutral by pumping out the protons previously leaked into the cells according to the steep pH gradient. The H+ pump is driven by the plasma membrane ATPase, utilizing intracellular ATP produced by both oxidative phosphorylation and cyclic photophosphorylation via photosystem I. We also describe the characteristics and function of the two photosystems, Photosystem I (PSI) and II (PSII), in Cyanidium caldarium in comparison with those of cyanobacteria, other eukaryotic algae, and higher plants, based on the crystal structures of the two complexes reported so far

Global Inorganic Source of Atmospheric Bromine

A few bromine molecules per trillion (ppt) causes the complete destruction of ozone in the lower troposphere during polar spring and about half of the losses associated with the “ozone hole” in the stratosphere. Recent field and aerial measurements of the proxy BrO in the free troposphere suggest an even more pervasive global role for bromine. Models, which quantify ozone trends by assuming atmospheric inorganic bromine (Br_y) stems exclusively from long-lived bromoalkane gases, significantly underpredict BrO measurements. This discrepancy effectively implies a ubiquitous tropospheric background level of ∼4 ppt Br_y of unknown origin. Here, we report that I^- efficiently catalyzes the oxidation of Br^- and Cl^- in aqueous nanodroplets exposed to ozone, the everpresent atmospheric oxidizer, under conditions resembling those encountered in marine aerosols. Br^- and Cl^-, which are rather unreactive toward O_3 and were previously deemed unlikely direct precursors of atmospheric halogens, are readily converted into IBr_2^- and ICl_2^- en route to Br_2(g) and Cl_2(g) in the presence of I^-. Fine sea salt aerosol particles, which are predictably and demonstrably enriched in I^- and Br^-, are thus expected to globally release photoactive halogen compounds into the atmosphere, even in the absence of sunlight

Anion-Catalyzed Dissolution of NO_2 on Aqueous Microdroplets

Fifty-seven years after NOx (NO + NO_2) were identified as essential components of photochemical smog, atmospheric chemical models fail to correctly predict •OH/HO_2• concentrations under NO_x-rich conditions. This deficiency is due, in part, to the uncertain rates and mechanism for the reactive dissolution of NO_2(g) (2NO_2 + H_2O = NO_3^− + H^+ + HONO) in fog and aerosol droplets. Thus, state-of-the-art models parametrize the uptake of NO_2 by atmospheric aerosol from data obtained on “deactivated tunnel wall residue”. Here, we report experiments in which NO_3^− production on the surface of microdroplets exposed to NO_2(g) for 1 ms is monitored by online thermospray mass spectrometry. NO_2 does not dissolve in deionized water (NO_3^− signals below the detection limit) but readily produces NO_3^− on aqueous NaX (X = Cl, Br, I) microdroplets with NO_2 uptake coefficients γ that vary nonmonotonically with electrolyte concentration and peak at γ_(max) ~ 10^(−4) for [NaX] ~ 1 mM, which is >10^3 larger than that in neat water. Since I^− is partially oxidized to I_2•^− in this process, anions seem to capture NO2(g) into X−NO_2•^− radical anions for further reaction at the air/water interface. By showing that γ is strongly enhanced by electrolytes, these results resolve outstanding discrepancies between previous measurements in neat water versus NaCl-seeded clouds. They also provide a general mechanism for the heterogeneous conversion of NO_2(g) to (NO_3^− + HONO) on the surface of aqueous media