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Santa Barbara, CA, United States

Edwards D.T.,University of California at Santa Barbara | Takahashi S.,University of Southern California | Sherwin M.S.,University of California at Santa Barbara | Sherwin M.S.,Institute for Terahertz Science and Technology | And 2 more authors.
Journal of Magnetic Resonance | Year: 2012

At 8.5 T, the polarization of an ensemble of electron spins is essentially 100% at 2 K, and decreases to 30% at 20 K. The strong temperature dependence of the electron spin polarization between 2 and 20 K leads to the phenomenon of spin bath quenching: temporal fluctuations of the dipolar magnetic fields associated with the energy-conserving spin "flip-flop" process are quenched as the temperature of the spin bath is lowered to the point of nearly complete spin polarization. This work uses pulsed electron paramagnetic resonance (EPR) at 240 GHz to investigate the effects of spin bath quenching on the phase memory times (T M) of randomly-distributed ensembles of nitroxide molecules below 20 K at 8.5 T. For a given electron spin concentration, a characteristic, dipolar flip-flop rate (W) is extracted by fitting the temperature dependence of T M to a simple model of decoherence driven by the spin flip-flop process. In frozen solutions of 4-Amino-TEMPO, a stable nitroxide radical in a deuterated water-glass, a calibration is used to quantify average spin-spin distances as large as r̄=6.6nm from the dipolar flip-flop rate. For longer distances, nuclear spin fluctuations, which are not frozen out, begin to dominate over the electron spin flip-flop processes, placing an effective ceiling on this method for nitroxide molecules. For a bulk solution with a three-dimensional distribution of nitroxide molecules at concentration n, we find W∝n∝1/ r̄ 3, which is consistent with magnetic dipolar spin interactions. Alternatively, we observe W∝n3 2 for nitroxides tethered to a quasi two-dimensional surface of large (O ∼ 200 nm), unilamellar, lipid vesicles, demonstrating that the quantification of spin bath quenching can also be used to discern the geometry of molecular assembly or organization. © 2012 Elsevier Inc. All rights reserved.

Edwards D.T.,University of California at Santa Barbara | Ma Z.,Northwestern University | Meade T.J.,Northwestern University | Goldfarb D.,Weizmann Institute of Science | And 4 more authors.
Physical Chemistry Chemical Physics | Year: 2013

Interspin distances between 0.8 nm and 2.0 nm can be measured through the dipolar broadening of the continuous wave (cw) EPR spectrum of nitroxide spin labels at X-band (9.4 GHz, 0.35 T). We introduce Gd3+ as a promising alternative spin label for distance measurements by cw EPR above 7 Tesla, where the 1/2〉 to 1/2〉 transition narrows below 1 mT and becomes extremely sensitive to dipolar broadening. To estimate the distance limits of cw EPR with Gd3+, we have measured spectra of frozen solutions of GdCl 3 at 8.6 T (240 GHz) and 10 K at concentrations ranging from 50 mM to 0.1 mM, covering a range of average interspin distances. These experiments show substantial dipolar broadening at distances where line broadening cannot be observed with nitroxides at X-band. This data, and its agreement with calculated dipolar-broadened lineshapes, show Gd3+ to be sensitive to distances as long as ∼3.8 nm. Further, the linewidth of a bis-Gd3+ complex with a flexible ∼1.6 nm bridge is strongly broadened as compared to the mono-Gd3+ complex, demonstrating the potential for application to pairwise distances. Gd-DOTA-based chelates that can be functionalized to protein surfaces display linewidths narrower than aqueous GdCl3, implying they should be even more sensitive to dipolar broadening. Therefore, we suggest that the combination of tailored Gd3+ labels and high magnetic fields can extend the longest interspin distances measurable by cw EPR from 2.0 nm to 3.8 nm. cw EPR data at 260 K demonstrate that the line broadening remains clear out to similar average interspin distances, offering Gd3+ probes as promising distance rulers at temperatures higher than possible with conventional pulsed EPR distance measurements. © 2013 the Owner Societies.

Morris C.M.,University of California at Santa Barbara | Morris C.M.,Institute for Terahertz Science and Technology | Stehr D.,Institute for Terahertz Science and Technology | Stehr D.,Helmholtz Center Dresden | And 7 more authors.
Nano Letters | Year: 2012

"Quantum posts" are roughly cylindrical semiconductor nanostructures that are embedded in an energetically shallower "matrix" quantum well of comparable thickness. We report measurements of voltage-controlled charging and terahertz absorption of 30 nm thick InGaAs quantum wells and posts. Under flat-band (zero-electric field) conditions, the quantum posts each contain approximately six electrons, and an additional ∼2.4 × 10 11 cm -2 electrons populate the quantum well matrix. In this regime, absorption spectra show peaks at 3.5 and 4.8 THz (14 and 19 meV) whose relative amplitude depends strongly on temperature. These peaks are assigned to intersubband transitions of electrons in the quantum well matrix. A third, broader feature has a temperature-independent amplitude and is assigned to an absorption involving quantum posts. Eight-band k·p calculations incorporating the effects of strain and Coulomb repulsion predict that the electrons in the posts strongly repel the electrons in the quantum well matrix, "perforating" the electron gas. The strongest calculated transition, which has a frequency close to the center of the quantum post related absorption at 5 THz (20 meV), is an ionizing transition from a filled state to a quasi-bound state that can easily scatter to empty states in the quantum well matrix. © 2011 American Chemical Society.

Edwards D.T.,University of California at Santa Barbara | Zhang Y.,TU Munich | Glaser S.J.,TU Munich | Han S.,University of California at Santa Barbara | And 3 more authors.
Physical Chemistry Chemical Physics | Year: 2013

Electron paramagnetic resonance (EPR) powered by a free electron laser (FEL) has been shown to dramatically expand the capabilities of EPR at frequencies above ∼100 GHz, where other high-power sources are unavailable. High-power pulses are necessary to achieve fast (<10 ns) spin rotations in order to alleviate the limited excitation bandwidth and time resolution that typically hamper pulsed EPR at these high frequencies. While at these frequencies, an FEL is the only source that provides ∼1 kW of power and can be tuned continuously up to frequencies above 1 THz, it has only recently been implemented for one- and two-pulse EPR, and the capabilities of the FEL as an EPR source are still being expanded. This manuscript presents phase cycling of two pulses in an FEL-EPR spectrometer operating at 240 GHz. Given that the FEL, unlike amplifiers, cannot be easily phase-locked to a reference source, we instead apply retrospective data processing to measure the relative phase of each FEL pulse in order to correct the signal phase accordingly. This allows the measured signal to be averaged coherently, and the randomly changing phase of the FEL pulse results in a stochastic phase cycle, which, in the limit of many pulses, efficiently cancels artifacts and improves sensitivity. Further, the relative phase between the first and second pulse, which originates from the difference in path length traversed by each pulse, can be experimentally measured without phase-sensitive detection. We show that the relative phase of the two pulses can be precisely tuned, as well as distinctly switched by a fixed amount, with the insertion of a dielectric material into the quasi-optical path of one of the pulses. Taken together, these techniques offer many of the advantages of arbitrary phase control, and allow application of phase cycling to dramatically enhance signal quality in pulsed EPR experiments utilizing high-power sources that cannot be phase-locked. © 2013 the Owner Societies.

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