Vacuum-UV negative photoion spectroscopy of CF3Cl, CF3Br and CF3I

Using synchrotron radiation negative ions have been detected by mass spectrometry following vacuum-UV photoexcitation of trifluorochloromethane (CF$_3$Cl), trifluorobromomethane (CF$_3$Br) and trifluoroiodomethane (CF$_3$I). The anions F$^-$, X$^-$, F$_2^-$, FX$^-$, CF$^-$, CF$_2^-$ and CF$_3^-$ were observed from all three molecules, where X = Cl, Br or I, and their ion yields recorded in the range 8-35 eV. With the exception of Br$^-$ and I$^-$, the anions observed show a linear dependence of signal with pressure, showing that they arise from unimolecular ion-pair dissociation. Dissociative electron attachment, following photoionization of CF$_3$Br and CF$_3$I as the source of low-energy electrons, is shown to dominate the observed Br$^-$ and I$^-$ signals, respectively. Cross sections for ion-pair formation are put on to an absolute scale by calibrating the signal strengths with those of F$^-$ from both SF$_6$ and CF$_4$. These anion cross sections are normalized to vacuum-UV absorption cross sections, where available, and the resulting quantum yields are reported. Anion appearance energies are used to calculate upper limits to 298 K bond dissociation energies for $D^0$(CF$_3$-X) which are consistent with literature values. We report new data for $D^0$(CF$_2$I$^-$-F) ≤ 2.7 ± 0.2 eV and $\Delta_fH^0_{298}$ (CF$_2$I$^+$) ≤ (598 ± 22) kJ mol$^{-1}$. No ion-pair formation is observed below the ionization energy of the parent molecule for CF$_3$Cl and CF$_3$Br, and only weak signals (in both I$^-$ and F$^-$) are detected for CF$_3$I. These observations suggest neutral photodissociation is the dominant exit channel to Rydberg state photoexcitation at these lower energies

Dissociative Autoionization in (1+2)-photon Above Threshold Excitation of H2 Molecules

We have theoretically studied the effect of dissociative autoionization on the photoelectron energy spectrum in (1+2)-photon above threshold ionization(ATI) of H2 molecules. We have considered excitation from the ground state X-singlet-Sigma-g+(v=0,j) to the doubly excited autoionizing states of singlet-Sigma-u+ and singlet-Pi-u+ symmetry, via the intermediate resonant B-singlet-Sigma-u+(v=5,j) states. We have shown that the photoelectron energy spectrum is oscillatory in nature and shows three distinct peaks above the photoelectron energy 0.7 eV. This feature has been observed in a recent experiment by Rottke et al, J. Phys. B, Vol. 30, p-4049 (1997).Comment: 11 pages and 4 figure

Cognitive performance profiles by latent classes of drug use

Background and Objectives: The relationship between substance use and cognitive deficits is complex and requires innovative methods to enhance understanding. The present study is the first to use LCA to examine associations of drug use patterns with cognitive performance. Methods: Cocaine/heroin users (N = 552) completed questionnaires, and cognitive measures. LCA identified classes based on past-month drug use and adjusted for probabilities of group membership when examining cognitive performance. Latent indicators were: alcohol (ALC), cigarettes (CIG), marijuana (MJ), crack smoking (CS), nasal heroin (NH), injection cocaine (IC), injection heroin (IH), and injection speedball (IS). Age and education were included as covariates in model creation. Results: Bootstrap likelihood ratio test (BLRT) supported a 5-class model. Prevalent indicators (estimated probability of over 50%) for each class are as follows: “Older Nasal Heroin/Crack Smokers” (ONH/CS, n = 166.9): ALC, CIG, NH, CS; “Older, Less Educated Polysubstance” (OLEP, n = 54.8): ALC, CIG, CS, IH, IC, and IS; “Younger Multi-Injectors” (MI, n = 128.7): ALC, CIG, MJ, IH, IC, and IS; “Less Educated Heroin Injectors” (LEHI, n = 87.4): CIG, IH; and “More Educated Nasal Heroin” users (MENH, n = ALC, CIG, NH. In general, all classes performed worse than established norms and older, less educated classes performed worse, with the exception that MENH demonstrated worse cognitive flexibility than YMI. Discussion and Conclusions: This study demonstrated novel applications of a methodology for examining complicated relationships between polysubstance use and cognitive performance. Scientific Significance: Education and/or nasal heroin use are associated with reduced cognitive flexibility in this sample of inner city drug users

Cm-Wavelength Total Flux and Linear Polarization Properties of Radio-Loud BL Lacertae Objects

Results from a long-term program to quantify the range of behavior of the cm-wavelength total flux and linear polarization variability properties of a sample of 41 radio-loud BL Lac objects using weekly to tri-monthly observations with the University of Michigan 26-m telescope operating at 14.5, 8.0, and 4.8 GHz are presented; these observations are used to identify class-dependent differences between these BL Lacs and QSOs in the Pearson-Readhead sample. The BL Lacs are found to be more highly variable in total flux density than the QSOs, exhibiting changes that are often nearly-simultaneous and of comparable amplitude at 14.5 and 4.8 GHz in contrast to the behavior in the QSOs and supporting the existence of class-dependent differences in opacity within the parsec-scale jet flows. Structure function analyses of the flux observations quantify that a characteristic timescale is identifiable in only 1/3 of the BL Lacs. The time-averaged fractional linear polarizations are only on the order of a few percent and are consistent with the presence of tangled magnetic fields within the emitting regions. In many sources a preferred long-term orientation of the EVPA is present; when compared with the VLBI structural axis, no preferred position angle difference is identified. The polarized flux typically exhibits variability with timescales of months to a few years and shows the signature of a propagating shock during several resolved outbursts. The observations indicate that the source emission is predominately due to evolving source components and support the occurrence of more frequent shock formation in BL Lac parsec-scale flows than in QSO jets. The differences in variability behavior and polarization between BL Lacs and QSOs can be explained by differences in jet stability.Comment: 1 LaTex (aastex) file, 21 postscript figure files, 2 external LaTex table files. To appear in the Astrophysical Journa

What Does It Take? California County Funding Requests for Recovery-Oriented Full Service Partnerships Under the Mental Health Services Act

The need to move mental health systems toward more recovery-oriented treatment modes is well established. Progress has been made to define needed changes but evidence is lacking about the resources required to implement them. The Mental Health Services Act (MHSA) in California was designed to implement more recovery-oriented treatment modes. We use data from county funding requests and annual updates to examine how counties budgeted for recovery-oriented programs targeted to different age groups under MHSA. Findings indicate that initial per-client budgeting for Full Services Partnerships under MHSA was maintained in future cycles and counties budgeted less per client for children. With this analysis, we begin to benchmark resource allocation for programs that are intended to be recovery-oriented, which should be evaluated against appropriate outcome measures in the future to determine the degree of recovery-orientation

The New Element Californium (Atomic Number 98)

Definite identification has been made of an isotope of the element with atomic number 98 through the irradiation of Cm{sup 242} with about 35-Mev helium ions in the Berkeley Crocker Laboratory 60-inch cyclotron. The isotope which has been identified has an observed half-life of about 45 minutes and is thought to have the mass number 244. The observed mode of decay of 98{sup 244} is through the emission of alpha-particles, with energy of about 7.1 Mev, which agrees with predictions. Other considerations involving the systematics of radioactivity in this region indicate that it should also be unstable toward decay by electron capture. The chemical separation and identification of the new element was accomplished through the use of ion exchange adsorption methods employing the resin Dowex-50. The element 98 isotope appears in the eka-dysprosium position on elution curves containing berkelium and curium as reference points--that is, it precedes berkelium and curium off the column in like manner that dysprosium precedes terbium and gadolinium. The experiments so far have revealed only the tripositive oxidation state of eka-dysprosium character and suggest either that higher oxidation states are not stable in aqueous solutions or that the rates of oxidation are slow. The successful identification of so small an amount of an isotope of element 98 was possible only through having made accurate predictions of the chemical and radioactive properties

Kinetic detection of osmium(VI) ester intermediates during the OsO4‐mediated aqueous dihydroxylation of chloroethylenes

The kinetics and mechanism of the cis dihydroxylation of cis‐1,2‐ dichloroethylene, trans‐1,2‐dichloroethylene, and trichloroethylene by osmium tetroxide was studied systematically in aqueous solution. The stoichiometry of the process was determined based on the principle of continuous variation of reactant ratios with spectrophotometric detection. The results always showed 1:1 stoichiometry, which is in agreement with dihydroxylation. All three reactions were found to proceed in two distinct steps. The first step occurred on a time scale of seconds and was associated with a minor change in absorbance and was identified as the formation of a 1:1 adduct between the two reagents, which is the osmium(VI) ester that plays a decisive role in catalytic applications. This species is formed in an equilibrium that is very much shifted toward the reactants, so the osmium(VI) complex is a short‐lived intermediate of the process, which is detected kinetically, but its concentration is never high enough for structural characterization. The second reaction is accompanied by major spectral changes; it involves the formation of the final products. Our results clearly show that it is possible to detect the intermediate of the process by careful kinetic studies. It is also possible that the same strategy might be successful in other OsO4‐dependent dihydroxylation processes

Three-flavour neutrino oscillation update

We review the present status of three-flavour neutrino oscillations, taking into account the latest available neutrino oscillation data presented at the Neutrino 2008 Conference. This includes the data released this summer by the MINOS collaboration, the data of the neutral current counter phase of the SNO solar neutrino experiment, as well as the latest KamLAND and Borexino data. We give the updated determinations of the leading 'solar' and 'atmospheric' oscillation parameters. We find from global data that the mixing angle $\theta_{13}$ is consistent with zero within $0.9\sigma$ and we derive an upper bound of $\sin^2\theta_{13} < 0.035 (0.056)$ at 90% CL (3$\sigma$).Comment: 17 pages, 7 figures. An appendix is added providing three-neutrino parameter determinations as of February 2010. We include all oscillation data, such as the first MINOS electron neutrino appearance data, the low energy threshold analysis given by the SNO Collaboration, as well as recently updated Standard Solar Model

Simultaneous assessment of acidogenesis-mitigation and specific bacterial growth-inhibition by dentifrices

Dentifrices can augment oral hygiene by inactivating bacteria and at sub-lethal concentrations may affect bacterial metabolism, potentially inhibiting acidogenesis, the main cause of caries. Reported herein is the development of a rapid method to simultaneously measure group-specific bactericidal and acidogenesis-mitigation effects of dentifrices on oral bacteria. Saliva was incubated aerobically and anaerobically in Tryptone Soya Broth, Wilkins-Chalgren Broth with mucin, or artificial saliva and was exposed to dentifrices containing triclosan/copolymer (TD); sodium fluoride (FD); stannous fluoride and zinc lactate (SFD1); or stannous fluoride, zinc lactate and stannous chloride (SFD2). Minimum inhibitory concentrations (MIC) were determined turbidometrically whilst group-specific minimum bactericidal concentrations (MBC) were assessed using growth media and conditions selective for total aerobes, total anaerobes, streptococci and Gram-negative anaerobes. Minimum acid neutralization concentration (MNC) was defined as the lowest concentration of dentifrice at which acidification was inhibited. Differences between MIC and MNC were calculated and normalized with respect to MIC to derive the combined inhibitory and neutralizing capacity (CINC), a cumulative measure of acidogenesis-mitigation and growth inhibition. The overall rank order for growth inhibition potency (MIC) under aerobic and anaerobic conditions was: TD> SFD2> SFD1> FD. Acidogenesis-mitigation (MNC) was ordered; TD> FD> SFD2> SFD1. CINC was ordered TD> FD> SFD2> SFD1 aerobically and TD> FD> SFD1> SFD2 anaerobically. With respect to group-specific bactericidal activity, TD generally exhibited the greatest potency, particularly against total aerobes, total anaerobes and streptococci. This approach enables the rapid simultaneous evaluation of acidity mitigation, growth inhibition and specific antimicrobial activity by dentifrices