198 research outputs found
Dangling-bond spin relaxation and magnetic 1/f noise from the amorphous-semiconductor/oxide interface: Theory
We propose a model for magnetic noise based on spin-flips (not
electron-trapping) of paramagnetic dangling-bonds at the
amorphous-semiconductor/oxide interface. A wide distribution of spin-flip times
is derived from the single-phonon cross-relaxation mechanism for a
dangling-bond interacting with the tunneling two-level systems of the amorphous
interface. The temperature and frequency dependence is sensitive to three
energy scales: The dangling-bond spin Zeeman energy delta, as well as the
minimum (E_min) and maximum (E_max) values for the energy splittings of the
tunneling two-level systems. We compare and fit our model parameters to a
recent experiment probing spin coherence of antimony donors implanted in
nuclear-spin-free silicon [T. Schenkel {\it et al.}, Appl. Phys. Lett. 88,
112101 (2006)], and conclude that a dangling-bond area density of the order of
10^{14}cm^{-2} is consistent with the data. This enables the prediction of
single spin qubit coherence times as a function of the distance from the
interface and the dangling-bond area density in a real device structure. We
apply our theory to calculations of magnetic flux noise affecting SQUID devices
due to their Si/SiO_2 substrate. Our explicit estimates of flux noise in SQUIDs
lead to a noise spectral density of the order of 10^{-12}Phi_{0}^{2} {Hz}^{-1}
at f=1Hz. This value might explain the origin of flux noise in some SQUID
devices. Finally, we consider the suppression of these effects using surface
passivation with hydrogen, and the residual nuclear-spin noise resulting from a
perfect silicon-hydride surface.Comment: Final published versio
Electron Spin-Relaxation Times of Phosphorus Donors in Silicon
Pulsed electron paramagnetic resonance measurements of donor electron spins
in natural phosphorus-doped silicon (Si:P) and isotopically-purified 28Si:P
show a strongly temperature-dependent longitudinal relaxation time, T1, due to
an Orbach process with DeltaE = 126 K. The 2-pulse echo decay is exponential in
28Si:P, with the transverse relaxation (decoherence) time, T2, controlled by
the Orbach process above ~12 K and by instantaneous diffusion at lower
temperatures. Spin echo experiments with varying pulse turning angles show that
the intrinsic T2 of an isolated spin in 28Si:P is ~60 ms at 7 K.Comment: Submitted to PRL on 02.28.200
Overcoming artificial broadening in GdÂłâșâGdÂłâș distance distributions arising from dipolar pseudo-secular terms in DEER experiments
By providing accurate distance measurements between spin labels site-specifically attached to bio-macromolecules, double electronâelectron resonance (DEER) spectroscopy provides a unique tool to probe the structural and conformational changes in these molecules. Gd3+-tags present an important family of spin-labels for such purposes, as they feature high chemical stability and high sensitivity in high-field DEER measurements. The high sensitivity of the Gd3+ ion is associated with its high spin (S = 7/2) and small zero field splitting (ZFS), resulting in a narrow spectral width of its central transition at high fields. However, under the conditions of short distances and exceptionally small ZFS, the weak coupling approximation, which is essential for straightforward DEER data analysis, becomes invalid and the pseudo-secular terms of the dipolar Hamiltonian can no longer be ignored. This work further explores the effects of pseudo-secular terms on Gd3+âGd3+ DEER measurements using a specifically designed ruler molecule; a rigid bis-Gd3+-DOTA model compound with an expected Gd3+âGd3+ distance of 2.35 nm and a very narrow central transition at the W-band (95 GHz). We show that the DEER dipolar modulations are damped under the standard W-band DEER measurement conditions with a frequency separation, ÎÎœ, of 100 MHz between the pump and observe pulses. Consequently, the DEER spectrum deviates considerably from the expected Pake pattern. We show that the Pake pattern and the associated dipolar modulations can be restored with the aid of a dual mode cavity by increasing ÎÎœ from 100 MHz to 1.09 GHz, allowing for a straightforward measurement of a Gd3+âGd3+ distance of 2.35 nm. The increase in ÎÎœ increases the contribution of the |â5/2ă â |â3/2ă and |â7/2ă â |â5/2ă transitions to the signal at the expense of the |â3/2 ă â |â1/2ă transition, thus minimizing the effect of dipolar pseudo-secular terms and restoring the validity of the weak coupling approximation. We apply this approach to the A93C/N140C mutant of T4 lysozyme labeled with two different Gd3+ tags that have narrow central transitions and show that even for a distance of 4 nm there is still a significant (about two-fold) broadening that is removed by increasing ÎÎœ to 636 MHz and 898 MHz.This research was supported by the Israeli Science Foundation (grant
334/14) and made possible in part by the historic generosity of the
Harold Perlman Family. D. G. holds the Erich Klieger professorial
chair in Chemical Physic
Electron spin dynamics in quantum dots and related nanostructures due to hyperfine interaction with nuclei
We review and summarize recent theoretical and experimental work on electron
spin dynamics in quantum dots and related nanostructures due to hyperfine
interaction with surrounding nuclear spins. This topic is of particular
interest with respect to several proposals for quantum information processing
in solid state systems. Specifically, we investigate the hyperfine interaction
of an electron spin confined in a quantum dot in an s-type conduction band with
the nuclear spins in the dot. This interaction is proportional to the square
modulus of the electron wave function at the location of each nucleus leading
to an inhomogeneous coupling, i.e. nuclei in different locations are coupled
with different strength. In the case of an initially fully polarized nuclear
spin system an exact analytical solution for the spin dynamics can be found.
For not completely polarized nuclei, approximation-free results can only be
obtained numerically in sufficiently small systems. We compare these exact
results with findings from several approximation strategies.Comment: 26 pages, 9 figures. Topical Review to appear in J. Phys.: Condens.
Matte
Hyperfine coupling constants on innerâsphere water molecules of GdIIIâbased MRI contrast agents
[Abstract] Herein we present a theoretical investigation of the hyperfine coupling constants (HFCCs) on the innerâsphere water molecules of [Gd(H2O)8]3+ and different GdIIIâbased magnetic resonance imaging contrast agents such as [Gd(DOTA)(H2O)]â, [Gd(DTPA)(H2O)]2â, [Gd(DTPAâBMA)(H2O)] and [Gd(HPâDO3A)(H2O)]. DFT calculations performed on the [Gd(H2O)8]3+ model system show that both hybridâGGA functionals (BH&HLYP, B3PW91 and PBE1PBE) and the hybrid metaâGGA functional TPSSh provide 17O HFCCs in close agreement with the experimental data. The use of allâelectron relativistic approaches based on the DKH2 approximation and the use of relativistic effective core potentials (RECP) provide results of essentially the same quality. The accurate calculation of HFCCs on the [Gd(DOTA)(H2O)]â, [Gd(DTPA)(H2O)]2â, [Gd(DTPAâBMA)(H2O)] and [Gd(HPâDO3A)(H2O)] complexes requires an adequate description of solvent effects. This was achieved by using a mixed cluster/continuum approach that includes explicitly two secondâsphere water molecules. The calculated isotropic 17O HFCCs (Aiso) fall within the range 0.40â0.56 MHz, and show deviations from the corresponding experimental values typically lower than 0.05 MHz. The Aiso values are significantly affected by the distance between the oxygen atom of the coordinated water molecule and the GdIII ion, as well as by the orientation of the water molecule plane with respect to the GdâO vector. 1H HFCCs of coordinated water molecules and 17O HFCCs of secondâsphere water molecules take values close to zero.Ministerio de EducaciĂłn y Ciencia; CTQ2009â10721Xunta de Galicia; IN845Bâ2010/06
Sulfite : Cytochrome c oxidoreductase from Thiobacillus novellus - Purification, characterization, and molecular biology of a heterodimeric member of the sulfite oxidase family
Direct oxidation of sulfite to sulfate occurs in various photo- and chemotrophic sulfur oxidizing microorganisms as the final step in the oxidation of reduced sulfur compounds and is catalyzed by sulfite:cytochrome c oxidoreductase (EC 1.8.2.1), Here we show that the enzyme from Thiobacillus novellus is a periplasmically located alpha beta heterodimer, consisting of a 40.6-kDa subunit containing a molybdenum cofactor and an 8.8-kDa monoheme cytochrome c(552) smbunit (midpoint redox potential, Em(8.0) = +280 mV), The organic component of the molybdenum cofactor was identified as molybdopterin contained in a 1:1 ratio to the Mo content of the enzyme. Electron paramagnetic resonance spectroscopy revealed the presence of a sulfite-inducible Mo(V) signal characteristic of sulfite:acceptor oxidoreductases. However, pH-dependent changes in the electron paramagnetic resonance signal were not detected. Kinetic studies showed that the enzyme exhibits a ping-pong mechanism involving two reactive sites. K-m values for sulfite and cytochrome c(550) were determined to be 27 and 4 mu M, respectively; the enzyme was found to be reversibly inhibited by sulfate and various buffer ions. The sorAB genes, which encode the enzyme, appear to form an operon, which is preceded by a putative extracytoplasmic function-type promoter and contains a hairpin loop termination structure downstream of sorB. While SorA exhibits significant similarities to known sequences of eukaryotic and bacterial sulfite:acceptor oxidoreductases, SorB does not appear to be closely related to any known c-type cytochromes
Probing Flexibility in Porphyrin-Based Molecular Wires Using Double Electron Electron Resonance
A series of butadiyne-linked zinc porphyrin oligomers, with one, two, three, and four porphyrin units and lengths of up to 75 angstrom, have been spin-labeled at both ends with stable nitroxide TEMPO radicals. The pulsed EPR technique of double electron electron resonance (DEER) was used to probe the distribution of intramolecular end-to-end distances, under a range of conditions. DEER measurements were carried out at 50 K in two types of dilute solution glasses: deutero-toluene (with 10% deutero-pyridine) and deutero-o-terphenyl (with 5% 4-benzyl pyridine). The complexes of the porphyrin oligomers with monodentate ligands (pyridine or 4-benzyl pyridine) principally adopt linear conformations. Nonlinear conformations are less populated in the lower glass-transition temperature solvent. When the oligomers bind star-shaped multidentate ligands, they are forced to bend into nonlinear geometries, and the experimental end-to-end distances for these complexes match those from molecular mechanics calculations. Our results show that porphyrin-based molecular wires are shape-persistent, and yet that their shapes can deformed by binding to multivalent ligands. Self-assembled ladder-shaped 2:2 complexes were also investigated to illustrate the scope of DEER measurements for providing structural information on synthetic noncovalent nanostructures
ChemInform Abstract: Electron Spin Echo Method as Used to Analyze the Spatial Distribution of Paramagnetic Centers
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