Muonium addition reactions in the gas phase: Quantum tunneling in Mu + C2H4 and Mu + C2D4

Copyright © 1990 American Institute of Physics.The reaction kinetics for the addition of the muonium (Mu=μ+e−) atom to C2H4 and C2D4 have been measured over the temperature range 150–500 K at (N2) moderator pressures near 1 atm. A factor of about 8 variation in moderator pressure was carried out for C2H4, with no significant change seen in the apparent rate constant kapp, which is therefore taken to be at the high pressure limit, yielding the bimolecular rate constant kMu for the addition step. This is also expected from the nature of the μSR technique employed, which, in favorable cases, gives kapp=kMu at any pressure. Comparisons with the H atom data of Lightfoot and Pilling, and Sugawara et al. and the D atom data of Sugawara et al. reveal large isotope effects. Only at the highest temperatures, near 500 K, is kMu/kH given by its classical value of 2.9, from the mean velocity dependence of the collision rate but at the lowest temperatures kMu/kH≳30/1 is seen, reflecting the pronounced tunneling of the much lighter Mu atom (mμ=1/9 mp). The present Mu results should provide accurate tests of reaction theories on currently available ab initio surfaces.NSERC (Canada), the Canada Council for their awarding of a Killam Research Fellowship and the Meson Science Institute, Faculty of Science, University of Tokyo

Experimental tests of reaction rate theory: Mu+H2 and Mu+D2

Copyright @ 1987 American Institute of Physics.Bimolecular rate constants for the thermal chemical reactions of muonium (Mu) with hydrogen and deuterium—Mu+H2→MuH+H and Mu+D2→MuD+D—over the temperature range 473–843 K are reported. The Arrhenius parameters and 1σ uncertainties for the H2 reaction are log A (cm3 molecule-1 s-1)=-9.605±0.074 and Ea =13.29±0.22 kcal mol-1, while for D2 the values are -9.67±0.12 and 14.73±0.40, respectively. These results are significantly more precise than those reported earlier by Garner et al. For the Mu reaction with H2 our results are in excellent agreement with the 3D quantum mechanical calculations of Schatz on the Liu–Siegbahn–Truhlar–Horowitz potential surface, but the data for both reactions compare less favorably with variational transition-state theory, particularly at the lower temperatures.NSERC (Canada) and the Petroleum Research Foundation of the Americal Chemical Society

Out-of-plane nesting driven spin spiral in ultrathin Fe/Cu(001) films

Epitaxial ultrathin Fe films on fcc Cu(001) exhibit a spin spiral (SS), in contrast to the ferromagnetism of bulk bcc Fe. We study the in-plane and out-of-plane Fermi surfaces (FSs) of the SS in 8 monolayer Fe/Cu(001) films using energy dependent soft x-ray momentum-resolved photoemission spectroscopy. We show that the SS originates in nested regions confined to out-of-plane FSs, which are drastically modified compared to in-plane FSs. From precise reciprocal space maps in successive zones, we obtain the associated real space compressive strain of 1.5+-0.5% along c-axis. An autocorrelation analysis quantifies the incommensurate ordering vector q=(2pi/a)(0,0,~0.86), favoring a SS and consistent with magneto-optic Kerr effect experiments. The results reveal the importance of in-plane and out-of-plane FS mapping for ultrathin films.Comment: 4 pages, 3 figure

Evidence for mass renormalization in LaNiO$"" sub 3_: an in situ soft x-ray photoemission study of epitaxial films

We investigate the electronic structure of high-quality single-crystal LaNiO$_3$ (LNO) thin films using in situ photoemission spectroscopy (PES). The in situ high-resolution soft x-ray PES measurements on epitaxial thin films reveal the intrinsic electronic structure of LNO. We find a new sharp feature in the PES spectra crossing the Fermi level, which is derived from the correlated Ni 3$d$ $e_g$ electrons. This feature shows significant enhancement of spectral weight with decreasing temperature. From a detailed analysis of resistivity data, the enhancement of spectral weight is attributed to increasing electron correlations due to antiferromagnetic fluctuations.Comment: 4 pages, 4 figures. submitted to Phys. Rev.

Temperature-Dependence of Magnetically-Active Charge Excitations in Magnetite across the Verwey Transition

We have studied the electronic structure of bulk single crystals and epitaxial films of magnetite Fe$_3$O$_4$. Fe $2p$ core-level spectra show clear differences between hard x-ray (HAX-) and soft x-ray (SX-) photoemission spectroscopy (PES), indicative of surface effects. The bulk-sensitive spectra exhibit temperature ($T$)-dependent charge excitations across the Verwey transition at $T_V$=122 K, which is missing in the surface-sensitive spectra. An extended impurity Anderson model full-multiplet analysis reveals roles of the three distinct Fe-species (A-Fe$^{3+}$, B-Fe$^{2+}$, B-Fe$^{3+}$) below $T_V$ for the Fe $2p$ spectra, and its $T-$dependent evolution. The Fe $2p$ HAXPES spectra show a clear magnetic circular dichroism (MCD) in the metallic phase of magnetized 100-nm-thick films. The model calculations also reproduce the MCD and identify the magnetically distinct sites associated with the charge excitations. Valence band HAXPES shows finite density of states at $E_F$ for the polaronic metal with remnant order above $T_V$, and a clear gap formation below $T_V$. The results indicate that the Verwey transition is driven by changes in the strongly correlated and magnetically active B-Fe$^{2+}$ and B-Fe$^{3+}$ electronic states, consistent with resistivity and bulk-sensitive optical spectra.Comment: 5 pages, 4 figures Accepted in Physical Review Letter

Temperature dependent Eu 3d-4f X-ray Absorption and Resonant Photoemission Study of the Valence Transition in EuNi2(Si0.2Ge0.8)2EuNi_2(Si_{0.2}Ge_{0.8})_2

We study the mixed valence transition ($T$$_{v}$ $\sim$80 K) in EuNi$_{2}$(Si$_{0.2}$Ge$_{0.8}$)$_{2}$ using Eu 3$d-4f$ X-ray absorption spectroscopy (XAS) and resonant photoemission spectroscopy (RESPES). The Eu$^{2+}$ and Eu$^{3+}$ main peaks show a giant resonance and the spectral features match very well with atomic multiplet calculations. The spectra show dramatic temperature ($T$)-dependent changes over large energies ($\sim$10 eV) in RESPES and XAS. The observed non-integral mean valencies of $\sim$2.35 $\pm$ 0.03 ($T$ = 120 K) and $\sim$2.70 $\pm$ 0.03 ($T$ = 40 K) indicate homogeneous mixed valence above and below $T$$_{v}$. The redistribution between Eu$^{2+}$$4f^7$+$[spd]^0$ and Eu$^{3+}$$4f^6$+$[spd]^1$ states is attributed to a hybridization change coupled to a Kondo-like volume collapse.Comment: 4 pages, 3 figure

Nanoscale Dichotomy of Ti 3d Carriers Mediating the Ferromagnetism in Co:TiO2 Anatase Thin Films

We study the surface and bulk electronic structure of the room-temperature ferromagnet Co:TiO2 anatase films using soft and hard x-ray photoemission spectroscopy with probe sensitivities of ~1 nm and ~10 nm, respectively. We obtain direct evidence of metallic Ti$^{3+}$ states in the bulk, which get suppressed to give a surface semiconductor, thus indicating a surface-bulk dichotomy. X-ray absorption and high-sensitivity resonant photoemission spectroscopy reveal Ti$^{3+}$ electrons at the Fermi level (E$_F$) and high-spin Co$^{2+}$ electrons occurring away from E$_F$. The results show the importance of the charge neutrality condition: Co$^{2+}$ + V$_{O}$$^{2-}$ + 2Ti$^{4+}$ $\leftrightarrow$ Co$^{2+}$ + 2Ti$^{3+}$ (V$_O$ is oxygen vacancy), which gives rise to the elusive Ti 3d carriers mediating ferromagnetism via the Co 3d-O 2p-Ti 3d exchange interaction pathway of the occupied orbitals.Comment: 4 pages, 4 figure

Evidence for a correlated insulator to antiferromagnetic metal transition in CrN

We investigate the electronic structure of Chromium Nitride (CrN) across the first-order magneto-structural transition at T_N ~ 286 K. Resonant photoemission spectroscopy shows a gap in the 3d partial density of states at the Fermi level and an On-site Coulomb energy U ~ 4.5 eV, indicating strong electron-electron correlations. Bulk-sensitive high resolution (6 meV) laser photoemission reveals a clear Fermi edge indicating an antiferromagnetic metal below T_N. Hard x-ray Cr 2p core-level spectra show T-dependent changes across T_N which originate from screening due to coherent states as substantiated by cluster model calculations using the experimentally observed U. The electrical resistivity confirms an insulator above T_N (E_g ~ 70 meV) which becomes a disordered metal below T_N. The results indicate CrN transforms from a correlated insulator to an antiferromagnetic metal, coupled to the magneto-structural transition.Comment: Submitted to Physical Review Letters (February 2010) 11 pages, 3 figures in the main text, 1 Supplementary Informatio