Surface stress of Ni adlayers on W(110): the critical role of the surface atomic structure

Puzzling trends in surface stress were reported experimentally for Ni/W(110) as a function of Ni coverage. In order to explain this behavior, we have performed a density-functional-theory study of the surface stress and atomic structure of the pseudomorphic and of several different possible 1x7 configurations for this system. For the 1x7 phase, we predict a different, more regular atomic structure than previously proposed based on surface x-ray diffraction. At the same time, we reproduce the unexpected experimental change of surface stress between the pseudomorphic and 1x7 configuration along the crystallographic surface direction which does not undergo density changes. We show that the observed behavior in the surface stress is dominated by the effect of a change in Ni adsorption/coordination sites on the W(110) surface.Comment: 14 pages, 3 figures Published in J. Phys.: Condens. Matter 24 (2012) 13500

Growth modes of Fe(110) revisited: a contribution of self-assembly to magnetic materials

We have revisited the epitaxial growth modes of Fe on W(110) and Mo(110), and propose an overview or our contribution to the field. We show that the Stranski-Krastanov growth mode, recognized for a long time in these systems, is in fact characterized by a bimodal distribution of islands for growth temperature in the range 250-700°C. We observe firstly compact islands whose shape is determined by Wulff-Kaischev's theorem, secondly thin and flat islands that display a preferred height, ie independant from nominal thickness and deposition procedure (1.4nm for Mo, and 5.5nm for W on the average). We used this effect to fabricate self-organized arrays of nanometers-thick stripes by step decoration. Self-assembled nano-ties are also obtained for nucleation of the flat islands on Mo at fairly high temperature, ie 800°C. Finally, using interfacial layers and solid solutions we separate two effects on the preferred height, first that of the interfacial energy, second that of the continuously-varying lattice parameter of the growth surface.Comment: 49 pages. Invited topical review for J. Phys.: Condens. Matte

Near-Infrared Kinetic Spectroscopy of the HO_2 and C_2H_5O_2 Self-Reactions and Cross Reactions

The self-reactions and cross reactions of the peroxy radicals HO_2 and C_2H_5O_2 and HO_2 were monitored using simultaneous independent spectroscopic probes to observe each radical species. Wavelength modulation (WM) near-infrared (NIR) spectroscopy was used to detect HO_2, and UV absorption monitored HO_2 and C_2H_5O_2. The temperature dependences of these reactions were investigated over a range of interest to tropospheric chemistry, 221−296 K. The Arrhenius expression determined for the cross reaction, k_2(T) = (6.01^(+1.95)_(−1.47)) × 10^(−13) exp((638 ± 73)/T) cm^3 molecules^(−1) s^(−1) is in agreement with other work from the literature. The measurements of the HO_2 self-reaction agreed with previous work from this lab and were not further refined.(1) The C_2H_5O_2 self-reaction is complicated by secondary production of HO_2. This experiment performed the first direct measurement of the self-reaction rate constant, as well as the branching fraction to the radical channel, in part by measurement of the secondary HO_2. The Arrhenius expression for the self-reaction rate constant is k_3(T) = (1.29^(+0.34)_(−0.27)) × 10^(−13)exp((−23 ± 61)/T) cm^3 molecules^(−1) s^(−1), and the branching fraction value is α = 0.28 ± 0.06, independent of temperature. These values are in disagreement with previous measurements based on end product studies of the branching fraction. The results suggest that better characterization of the products from RO_2 self-reactions are required

First principles calculation of structural and magnetic properties for Fe monolayers and bilayers on W(110)

Structure optimizations were performed for 1 and 2 monolayers (ML) of Fe on a 5 ML W(110) substrate employing the all-electron full-potential linearized augmented plane-wave (FP-LAPW) method. The magnetic moments were also obtained for the converged and optimized structures. We find significant contractions ($\sim$ 10 %) for both the Fe-W and the neighboring Fe-Fe interlayer spacings compared to the corresponding bulk W-W and Fe-Fe interlayer spacings. Compared to the Fe bcc bulk moment of 2.2 $\mu_B$, the magnetic moment for the surface layer of Fe is enhanced (i) by 15% to 2.54 $\mu_B$ for 1 ML Fe/5 ML W(110), and (ii) by 29% to 2.84 $\mu_B$ for 2 ML Fe/5 ML W(110). The inner Fe layer for 2 ML Fe/5 ML W(110) has a bulk-like moment of 2.3 $\mu_B$. These results agree well with previous experimental data

Factors determining recent changes of emissions of air pollutants in Europe

To support the European Commission in the review of the 2005 Thematic Strategy on Air Pollution, this report revisits the baseline scenario that was presented in 2005 in view of today's knowledge, in particular taking into account the impacts of the economic crisis on economic and energy development, and real-life experience with newly implemented emission regulations. It compares the final baseline emission projection developed in 2005 within the Clean Air For Europe (CAFE) programme for the Thematic Strategy on Air Pollution against the recent baseline projection prepared for the revision of the Thematic Strategy in 2012 (the TSAP-2012 baseline). The report reviews the assumptions on main drivers of emission changes, i.e., demographic trends, economic growth, changes in the energy intensity of GDP, switches to other fuels, and application of dedicated emission control measures. For most of these drivers, reality has developed rather different compared to what has been assumed in 2005. In reality, SO2 emissions in the old Member States in 2010 were 5% lower than what was projected by CAFE. NH3 was 10% and VOC 3% lower. NOx exceeded the CAFE projection by 7%, and PM2.5 by 10%. Larger differences occurred for the new Member States, where SO2 was 30% and NH3 16% below the levels suggest by CAFE. NOx was 11% higher, and PM2.5 and VOC 21% higher than estimated earlier. For 2020, the TSAP-2012 baseline projection expects for the EU-27 about 20% less SO2 emissions than the earlier CAFE baseline, with application of dedicated emission controls as the dominating factor for lower emissions. NOx would be 5-7% lower, depending on the assumptions on the effectiveness of the new vehicle emission standards. The PM projection is about 10% higher, while smaller differences emerge for VOC and NH3. Many of these changes are smaller than differences in the actual drivers. In many cases, higher effectiveness of dedicated emission controls compensated the lower than expected decline in total energy consumption as well as the delay in the phase-out of coal. A re-analysis of air pollution control costs based on the actual statistics suggests for 2010 6% higher costs earlier estimated, mainly due to higher consumption of coal that required more emission control efforts. For 2020, emissions of the new TSAP-2012 baseline (without additional measures) are substantially higher than the indicative targets for emission reductions established by the Thematic Strategy in 2005. As a consequence, the environmental targets established by the TSAP for the protection of human health, eutrophication and forest acidification would not be met by the TSAP-2012 baseline without additional measures

Spin-Peierls transition in TiOCl

Temperature-dependent x-ray diffraction of the low-dimensional spin 1/2 quantum magnet TiOCl shows that the phase transition at T_{c2} = 90 K corresponds to a lowering of the lattice symmetry. Below T_{c1} = 66 K a twofold superstructure develops, that indicates the formation of spin-singlet pairs via direct exchange between neighboring Ti atoms, while the role of superexchange is found to be negligible. TiOCl thus is identified as a spin-Peierls system of pure 1D chains of atoms. The first-order character of the transition at T_{c1} is explained by the competition between the structurally deformed state below T_{c2} and the spin-Peierls state below T_{c1}.Comment: Phys. Rev. B (Rapid Communications) in pres