Uncovering many-body correlations in nanoscale nuclear spin baths by central spin decoherence

PubMed Central

Ma, Wen-Long; Wolfowicz, Gary; Zhao, Nan; Li, Shu-Shen; Morton, John J.L.; Liu, Ren-Bao

2014-01-01

Central spin decoherence caused by nuclear spin baths is often a critical issue in various quantum computing schemes, and it has also been used for sensing single-nuclear spins. Recent theoretical studies suggest that central spin decoherence can act as a probe of many-body physics in spin baths; however, identification and detection of many-body correlations of nuclear spins in nanoscale systems are highly challenging. Here, taking a phosphorus donor electron spin in a 29Si nuclear spin bath as our model system, we discover both theoretically and experimentally that many-body correlations in nanoscale nuclear spin baths produce identifiable signatures in decoherence of the central spin under multiple-pulse dynamical decoupling control. We demonstrate that under control by an odd or even number of pulses, the central spin decoherence is principally caused by second- or fourth-order nuclear spin correlations, respectively. This study marks an important step toward studying many-body physics using spin qubits. PMID:25205440

J-GFT NMR for precise measurement of mutually correlated nuclear spin-spin couplings.

PubMed

Atreya, Hanudatta S; Garcia, Erwin; Shen, Yang; Szyperski, Thomas

2007-01-24

G-matrix Fourier transform (GFT) NMR spectroscopy is presented for accurate and precise measurement of chemical shifts and nuclear spin-spin couplings correlated according to spin system. The new approach, named "J-GFT NMR", is based on a largely extended GFT NMR formalism and promises to have a broad impact on projection NMR spectroscopy. Specifically, constant-time J-GFT (6,2)D (HA-CA-CO)-N-HN was implemented for simultaneous measurement of five mutually correlated NMR parameters, that is, 15N backbone chemical shifts and the four one-bond spin-spin couplings 13Calpha-1Halpha, 13Calpha-13C', 15N-13C', and 15N-1HNu. The experiment was applied for measuring residual dipolar couplings (RDCs) in an 8 kDa protein Z-domain aligned with Pf1 phages. Comparison with RDC values extracted from conventional NMR experiments reveals that RDCs are measured with high precision and accuracy, which is attributable to the facts that (i) the use of constant time evolution ensures that signals do not broaden whenever multiple RDCs are jointly measured in a single dimension and (ii) RDCs are multiply encoded in the multiplets arising from the joint sampling. This corresponds to measuring the couplings multiple times in a statistically independent manner. A key feature of J-GFT NMR, i.e., the correlation of couplings according to spin systems without reference to sequential resonance assignments, promises to be particularly valuable for rapid identification of backbone conformation and classification of protein fold families on the basis of statistical analysis of dipolar couplings.

Direct monitoring by carbon-13 nuclear magnetic resonance spectroscopy of the metabolism and metabolic rate of 13C-labeled compounds in vivo.

PubMed

Iida, K; Hidoh, O; Fukami, J; Kajiwara, M

1991-01-01

Carbon-13 nuclear magnetic resonance spectroscopy has been used to observe the transformations of [1-13C]-D-glucose to [1,1'-13C2]-D-trehalose, and [3-13C]-L-alanine to [2-13C]-L-glutamic acid in the living body of Gryllodes sigillatus. [3-13C]-D-Alanine was not metabolized. The metabolic rate of [1-13C]-D-glucose was found to be altered by prior injection of boric acid.

Electrical detection of nuclear spin-echo signals in an electron spin injection system

NASA Astrophysics Data System (ADS)

Lin, Zhichao; Rasly, Mahmoud; Uemura, Tetsuya

2017-06-01

We demonstrated spin echoes of nuclear spins in a spin injection device with a highly polarized spin source by nuclear magnetic resonance (NMR). Efficient spin injection into GaAs from a half-metallic spin source of Co2MnSi enabled efficient dynamic nuclear polarization (DNP) and sensitive detection of NMR signals even at a low magnetic field of ˜0.1 T and a relatively high temperature of 4.2 K. The intrinsic coherence time T2 of 69Ga nuclear spins was evaluated from the spin-echo signals. The relation between T2 and the decay time of the Rabi oscillation suggests that the inhomogeneous effects in our system are not obvious. This study provides an all-electrical NMR system for nuclear-spin-based qubits.

Nuclear spin-lattice relaxation in nitroxide spin-label EPR.

PubMed

Marsh, Derek

2016-11-01

Nuclear relaxation is a sensitive monitor of rotational dynamics in spin-label EPR. It also contributes competing saturation transfer pathways in T 1 -exchange spectroscopy, and the determination of paramagnetic relaxation enhancement in site-directed spin labelling. A survey shows that the definition of nitrogen nuclear relaxation rate W n commonly used in the CW-EPR literature for 14 N-nitroxyl spin labels is inconsistent with that currently adopted in time-resolved EPR measurements of saturation recovery. Redefinition of the normalised 14 N spin-lattice relaxation rate, b=W n /(2W e ), preserves the expressions used for CW-EPR, whilst rendering them consistent with expressions for saturation recovery rates in pulsed EPR. Furthermore, values routinely quoted for nuclear relaxation times that are deduced from EPR spectral diffusion rates in 14 N-nitroxyl spin labels do not accord with conventional analysis of spin-lattice relaxation in this three-level system. Expressions for CW-saturation EPR with the revised definitions are summarised. Data on nitrogen nuclear spin-lattice relaxation times are compiled according to the three-level scheme for 14 N-relaxation: T 1 n =1/W n . Results are compared and contrasted with those for the two-level 15 N-nitroxide system. Copyright © 2016 Elsevier Inc. All rights reserved.

Room-temperature in situ nuclear spin hyperpolarization from optically pumped nitrogen vacancy centres in diamond

DOE PAGES

King, Jonathan P.; Jeong, Keunhong; Vassiliou, Christophoros C.; ...

2015-12-07

Low detection sensitivity stemming from the weak polarization of nuclear spins is a primary limitation of magnetic resonance spectroscopy and imaging. Methods have been developed to enhance nuclear spin polarization but they typically require high magnetic fields, cryogenic temperatures or sample transfer between magnets. Here we report bulk, room-temperature hyperpolarization of 13C nuclear spins observed via high-field magnetic resonance. The technique harnesses the high optically induced spin polarization of diamond nitrogen vacancy centres at room temperature in combination with dynamic nuclear polarization. We observe bulk nuclear spin polarization of 6%, an enhancement of ~170,000 over thermal equilibrium. The signal ofmore » the hyperpolarized spins was detected in situ with a standard nuclear magnetic resonance probe without the need for sample shuttling or precise crystal orientation. In conclusion, hyperpolarization via optical pumping/dynamic nuclear polarization should function at arbitrary magnetic fields enabling orders of magnitude sensitivity enhancement for nuclear magnetic resonance of solids and liquids under ambient conditions.« less

Entanglement measures in embedding quantum simulators with nuclear spins

NASA Astrophysics Data System (ADS)

Xin, Tao; Pedernales, Julen S.; Solano, Enrique; Long, Gui-Lu

2018-02-01

We implement an embedding quantum simulator (EQS) in nuclear spin systems. The experiment consists of a simulator of up to three qubits, plus a single ancillary qubit, where we are able to efficiently measure the concurrence and the three-tangle of two-qubit and three-qubit systems as they undergo entangling dynamics. The EQS framework allows us to drastically reduce the number of measurements needed for this task, which otherwise would require full-state reconstruction of the qubit system. Our simulator is built of the nuclear spins of four 13C atoms in a molecule of trans-crotonic acid manipulated with NMR techniques.

Experimental investigation of vector static magnetic field detection using an NV center with a single first-shell 13C nuclear spin in diamond

NASA Astrophysics Data System (ADS)

Jiang, Feng-Jian; Ye, Jian-Feng; Jiao, Zheng; Jiang, Jun; Ma, Kun; Yan, Xin-Hu; Lv, Hai-Jiang

2018-05-01

We perform a proof-of-principle experiment that uses a single negatively charged nitrogen–vacancy (NV) color center with a nearest neighbor 13C nuclear spin in diamond to detect the strength and direction (including both polar and azimuth angles) of a static vector magnetic field by optical detection magnetic resonance (ODMR) technique. With the known hyperfine coupling tensor between an NV center and a nearest neighbor 13C nuclear spin, we show that the information of static vector magnetic field could be extracted by observing the pulsed continuous wave (CW) spectrum. Project supported by the National Natural Science Foundation of China (Grant Nos. 11305074, 11135002, and 11275083), the Key Program of the Education Department Outstanding Youth Foundation of Anhui Province, China (Grant No. gxyqZD2017080), and the Education Department Natural Science Foundation of Anhui Province, China (Grant No. KJHS2015B09).

Decoupling a hole spin qubit from the nuclear spins.

PubMed

Prechtel, Jonathan H; Kuhlmann, Andreas V; Houel, Julien; Ludwig, Arne; Valentin, Sascha R; Wieck, Andreas D; Warburton, Richard J

2016-09-01

A huge effort is underway to develop semiconductor nanostructures as low-noise hosts for qubits. The main source of dephasing of an electron spin qubit in a GaAs-based system is the nuclear spin bath. A hole spin may circumvent the nuclear spin noise. In principle, the nuclear spins can be switched off for a pure heavy-hole spin. In practice, it is unknown to what extent this ideal limit can be achieved. A major hindrance is that p-type devices are often far too noisy. We investigate here a single hole spin in an InGaAs quantum dot embedded in a new generation of low-noise p-type device. We measure the hole Zeeman energy in a transverse magnetic field with 10 neV resolution by dark-state spectroscopy as we create a large transverse nuclear spin polarization. The hole hyperfine interaction is highly anisotropic: the transverse coupling is <1% of the longitudinal coupling. For unpolarized, randomly fluctuating nuclei, the ideal heavy-hole limit is achieved down to nanoelectronvolt energies; equivalently dephasing times up to a microsecond. The combination of large and strong optical dipole makes the single hole spin in a GaAs-based device an attractive quantum platform.

Analyses of cocondensation of melamine and urea through formaldehyde with carbon 13 nuclear magnetic resonance spectroscopy

Treesearch

Tomita Bunchiro; Chung-Yun Hse

1995-01-01

The 13C-NMR (carbon 13 nuclear magnetic resonance) spectra of urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, and melamine-urea-formaldehyde (MUF) cocondensed resins synthesized under various conditions were taken with a frequency of 75 MHz. The main purpose was to investigate whether or not the occurrences of cocondensation...

Analysis of cocondensation of melamine and urea through formaldehyde with carbon 13 nuclear magnetic resonance spectroscopy

Treesearch

Bunichiro Tomita; Chung-Yun Hse

1995-01-01

The 13C-NMR (carbon 13 nuclear magnetic resonance) spectra of urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, and melamine-urea-formaldehyde (MUF) cocondensed resins synthesized under various conditions were taken with a frequency of 75 MHz. The main purpose was to investigate whether or not the occurrences of cocondensation...

Chemical and carbon-13 cross-polarization magic-angle spinning nuclear magnetic resonance characterization of logyard fines from British Columbia.

PubMed

Preston, C M; Forrester, P D

2004-01-01

Phasing out beehive burners and rising costs for landfilling have increased the need to widen options for utilization of the smaller size fractions of woody wastes generated during log handling and sawmilling in British Columbia. We characterized several size classes of logyard fines up to 16 mm sampled from coastal and interior operations. Total C, total N, ash, and condensed tannin concentrations were consistent with properties derived largely from wood, with varying proportions of bark and mixing with mineral soil. Especially for < 3-mm fractions, the latter resulted in high ash contents that would make them unsuitable for fuel. Solid-state 13C cross-polarization magic-angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectra were consistent with the chemical data, with high O-alkyl intensity and similarity to naturally occurring woody forest floor; no samples were high in aromatic or phenolic C. Aqueous extracts of two < 16-mm fines, which accounted for only a small proportion of the total C, were enriched in alkyl C and had low or undetectable tannins. Application to forest sites might cause short-term immobilization of N, but also might include possible longer-term benefits from reduction of N loss after harvesting and restoration of soil organic matter in degraded sites.

Resonant polarization transfer from electron spins to nuclear spins-or to muon spins-in semiconductors

NASA Astrophysics Data System (ADS)

Henstra, A.; Wenckebach, W. Th.

1991-02-01

A review is given of newly developed pulsed Electron Spin Resonance (ESR) methods for dynamic polarization of nuclear spins. The application of two of these methods, Nuclear Orientation Via Electron spin Locking (NOVEL) and the Integrated Solid Effect (ISE), for the polarization of nuclear spins in semiconductors is discussed in more detail. It is proposed to use these methods to study the ESR spectrum of unpaired electrons in the vicinity of muons that are bound in a solid. Thus, ESR would be observed with a sensitivity which is enhanced by about ten orders of magnitude compared to conventional ESR.

Structure of thin diamond films: A 1H and 13C nuclear-magnetic-resonance study

NASA Astrophysics Data System (ADS)

Pruski, M.; Lang, D. P.; Hwang, Son-Jong; Jia, H.; Shinar, J.

1994-04-01

The 1H and 13C nuclear magnetic resonance (NMR) of thin diamond films deposited from naturally abundant (1.1 at. %) as well as 50% and 100% 13enriched CH4 heavily diluted in H2 is described and discussed. Less than 0.6 at. % of hydrogen is found in the films which contain crystallites up to ~15 μm across. The 1H NMR consists of a broad 50-65-kHz-wide Gaussian line attributed to H atoms bonded to carbon and covering the crystallite surfaces. A narrow Lorentzian line was only occasionally observed and is found not to be intrinsic to the diamond structure. The 13C NMR demonstrates that >99.5% of the C atoms reside in a quaternary diamondlike configuration. 1-13C cross-polarization measurement indicates that, at the very least, the majority of 13C nuclei cross polarized by 1H, i.e., within three bond distances from a 1H at a crystallite surface, reside in sp3 diamondlike coordinated sites. The 13C relaxation rates of the films are four orders of magnitude faster than that of natural diamond and believed to be due to 13C spin diffusion to paramagnetic centers, presumably carbon dangling bonds. Analysis of the measured relaxation rates indicates that within the 13C spin-diffusion length of √DTc1 ~0.05 μm, these centers are uniformly distributed in the diamond crystallites. The possibility that the dangling bonds are located at internal nanovoid surfaces is discussed.

Optical Control of a Nuclear Spin in Diamond

NASA Astrophysics Data System (ADS)

Levonian, David; Goldman, Michael; Degreve, Kristiaan; Choi, Soonwon; Markham, Matthew; Twitchen, Daniel; Lukin, Mikhail

2017-04-01

The nitrogen-vacancy (NV) center in diamond has emerged as a promising candidate for quantum information and quantum communication applications. The NV center's potential as a quantum register is due to the long coherence time of its spin-triplet electronic ground state, the optical addressability of its electronic transitions, and the presence of nearby ancillary nuclear spins. The NV center's electronic spin and nearby nuclear spins are most commonly manipulated using applied microwave and RF fields, but this approach would be difficult to scale up for use with an array of NV-based quantum registers. In this context, all-optical manipulation would be more scalable, technically simpler, and potentially faster. Although all-optical control of the electronic spin has been demonstrated, it is an outstanding problem for the nuclear spins. Here, we use an optical Raman scheme to implement nuclear spin-specific control of the electronic spin and coherent control of the 14N nuclear spin.

Nuclear spin polarized H and D by means of spin-exchange optical pumping

NASA Astrophysics Data System (ADS)

Stenger, Jörn; Grosshauser, Carsten; Kilian, Wolfgang; Nagengast, Wolfgang; Ranzenberger, Bernd; Rith, Klaus; Schmidt, Frank

1998-01-01

Optically pumped spin-exchange sources for polarized hydrogen and deuterium atoms have been demonstrated to yield high atomic flow and high electron spin polarization. For maximum nuclear polarization the source has to be operated in spin temperature equilibrium, which has already been demonstrated for hydrogen. In spin temperature equilibrium the nuclear spin polarization PI equals the electron spin polarization PS for hydrogen and is even larger than PS for deuterium. We discuss the general properties of spin temperature equilibrium for a sample of deuterium atoms. One result are the equations PI=4PS/(3+PS2) and Pzz=PSṡPI, where Pzz is the nuclear tensor polarization. Furthermore we demonstrate that the deuterium atoms from our source are in spin temperature equilibrium within the experimental accuracy.

Nuclear spin noise in NMR revisited

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferrand, Guillaume; Luong, Michel; Huber, Gaspard

2015-09-07

The theoretical shapes of nuclear spin-noise spectra in NMR are derived by considering a receiver circuit with finite preamplifier input impedance and a transmission line between the preamplifier and the probe. Using this model, it becomes possible to reproduce all observed experimental features: variation of the NMR resonance linewidth as a function of the transmission line phase, nuclear spin-noise signals appearing as a “bump” or as a “dip” superimposed on the average electronic noise level even for a spin system and probe at the same temperature, pure in-phase Lorentzian spin-noise signals exhibiting non-vanishing frequency shifts. Extensive comparisons to experimental measurementsmore » validate the model predictions, and define the conditions for obtaining pure in-phase Lorentzian-shape nuclear spin noise with a vanishing frequency shift, in other words, the conditions for simultaneously obtaining the spin-noise and frequency-shift tuning optima.« less

Liquid-state nuclear spin comagnetometers.

PubMed

Ledbetter, M P; Pustelny, S; Budker, D; Romalis, M V; Blanchard, J W; Pines, A

2012-06-15

We discuss nuclear spin comagnetometers based on ultralow-field nuclear magnetic resonance in mixtures of miscible solvents, each rich in a different nuclear spin. In one version thereof, Larmor precession of protons and 19F nuclei in a mixture of thermally polarized pentane and hexafluorobenzene is monitored via a sensitive alkali-vapor magnetometer. We realize transverse relaxation times in excess of 20 s and suppression of magnetic field fluctuations by a factor of 3400. We estimate it should be possible to achieve single-shot sensitivity of about 5×10(-9)  Hz, or about 5×10(-11)  Hz in ≈1 day of integration. In a second version, spin precession of protons and 129Xe nuclei in a mixture of pentane and hyperpolarized liquid xenon is monitored using superconducting quantum interference devices. Application to spin-gravity experiments, electric dipole moment experiments, and sensitive gyroscopes is discussed.

Repetitive readout of a single electronic spin via quantum logic with nuclear spin ancillae.

PubMed

Jiang, L; Hodges, J S; Maze, J R; Maurer, P; Taylor, J M; Cory, D G; Hemmer, P R; Walsworth, R L; Yacoby, A; Zibrov, A S; Lukin, M D

2009-10-09

Robust measurement of single quantum bits plays a key role in the realization of quantum computation and communication as well as in quantum metrology and sensing. We have implemented a method for the improved readout of single electronic spin qubits in solid-state systems. The method makes use of quantum logic operations on a system consisting of a single electronic spin and several proximal nuclear spin ancillae in order to repetitively readout the state of the electronic spin. Using coherent manipulation of a single nitrogen vacancy center in room-temperature diamond, full quantum control of an electronic-nuclear system consisting of up to three spins was achieved. We took advantage of a single nuclear-spin memory in order to obtain a 10-fold enhancement in the signal amplitude of the electronic spin readout. We also present a two-level, concatenated procedure to improve the readout by use of a pair of nuclear spin ancillae, an important step toward the realization of robust quantum information processors using electronic- and nuclear-spin qubits. Our technique can be used to improve the sensitivity and speed of spin-based nanoscale diamond magnetometers.

Analysis of the transient response of nuclear spins in GaAs with/without nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Rasly, Mahmoud; Lin, Zhichao; Yamamoto, Masafumi; Uemura, Tetsuya

2016-05-01

As an alternative to studying the steady-state responses of nuclear spins in solid state systems, working within a transient-state framework can reveal interesting phenomena. The response of nuclear spins in GaAs to a changing magnetic field was analyzed based on the time evolution of nuclear spin temperature. Simulation results well reproduced our experimental results for the transient oblique Hanle signals observed in an all-electrical spin injection device. The analysis showed that the so called dynamic nuclear polarization can be treated as a cooling tool for the nuclear spins: It works as a provider to exchange spin angular momentum between polarized electron spins and nuclear spins through the hyperfine interaction, leading to an increase in the nuclear polarization. In addition, a time-delay of the nuclear spin temperature with a fast sweep of the external magnetic field produces a possible transient state for the nuclear spin polarization. On the other hand, the nuclear magnetic resonance acts as a heating tool for a nuclear spin system. This causes the nuclear spin temperature to jump to infinity: i.e., the average nuclear spins along with the nuclear field vanish at resonant fields of 75As, 69Ga and 71Ga, showing an interesting step-dip structure in the oblique Hanle signals. These analyses provide a quantitative understanding of nuclear spin dynamics in semiconductors for application in future computation processing.

Nuclear spin cooling by electric dipole spin resonance and coherent population trapping

NASA Astrophysics Data System (ADS)

Li, Ai-Xian; Duan, Su-Qing; Zhang, Wei

2017-09-01

Nuclear spin fluctuation suppression is a key issue in preserving electron coherence for quantum information/computation. We propose an efficient way of nuclear spin cooling in semiconductor quantum dots (QDs) by the coherent population trapping (CPT) and the electric dipole spin resonance (EDSR) induced by optical fields and ac electric fields. The EDSR can enhance the spin flip-flop rate and may bring out bistability under certain conditions. By tuning the optical fields, we can avoid the EDSR induced bistability and obtain highly polarized nuclear spin state, which results in long electron coherence time. With the help of CPT and EDSR, an enhancement of 1500 times of the electron coherence time can been obtained after a 500 ns preparation time.

13C-13C dipolar recoupling under very fast magic angle spinning in solid-state nuclear magnetic resonance: Applications to distance measurements, spectral assignments, and high-throughput secondary-structure determination

NASA Astrophysics Data System (ADS)

Ishii, Yoshitaka

2001-05-01

A technique is presented to recouple homonuclear dipolar couplings between dilute spin pairs such as 13C-13C systems under very fast magic angle spinning (MAS) in solid-state nuclear magnetic resonance (NMR) spectroscopy. The presented technique, finite pulse rf driven recoupling (fpRFDR), restores homonuclear dipolar interactions based on constructive usage of finite pulse-width effects in a phase- and symmetry-cycled π-pulse train in which a rotor-synchronous π pulse is applied every rotation period. The restored effective dipolar interaction has the form of a zero-quantum dipolar Hamiltonian for static solids, whose symmetry in spin space is different from that obtained by conventional rf driven recoupling (RFDR) techniques. It is demonstrated that the efficiency of recoupling by fpRFDR is not strongly dependent on chemical shift differences or resonance offsets in contrast to previous recoupling methods under very fast MAS. To realize distance measurements without effects of spin relaxation, a constant-time version of fpRFDR (CT-fpRFDR) is introduced, in which the effective evolution period is varied by refocusing dipolar evolution with a rotor-synchronized solid echo while the total recoupling period is kept constant. From CT-fpRFDR experiments at a spinning speed of 30.3 kHz in a field of 17.6 T, the 13C-13C distance of [1-13C]Ala-[1-13C]Gly-Gly was determined to be 3.27 Å, which agrees well with the value of 3.20 Å obtained by x-ray diffraction. Also, two-dimensional (2D) 13C/13C chemical-shift correlation NMR spectrum in a field of 9.4 T was obtained with fpRFDR for fibrils of the segmentally 13C- and 15N-labeled Alzheimer's β-Amyloid fragments, Aβ16-22 (residues 16-22 taken from the 40-residue Aβ peptide) in which Leu-17 through Ala-21 are uniformly 13C- and 15N-labeled. Most 13C resonances for the main chain as well as for the side chains are assigned based on 2D 13C/13C chemical-shift correlation patterns specific to amino-acid types. Examination

Amino Acid Selective 13C Labeling and 13C Scrambling Profile Analysis of Protein α and Side-Chain Carbons in Escherichia coli Utilized for Protein Nuclear Magnetic Resonance.

PubMed

Sugiki, Toshihiko; Furuita, Kyoko; Fujiwara, Toshimichi; Kojima, Chojiro

2018-06-20

Amino acid selective isotope labeling is an important nuclear magnetic resonance technique, especially for larger proteins, providing strong bases for the unambiguous resonance assignments and information concerning the structure, dynamics, and intermolecular interactions. Amino acid selective 15 N labeling suffers from isotope dilution caused by metabolic interconversion of the amino acids, resulting in isotope scrambling within the target protein. Carbonyl 13 C atoms experience less isotope scrambling than the main-chain 15 N atoms do. However, little is known about the side-chain 13 C atoms. Here, the 13 C scrambling profiles of the Cα and side-chain carbons were investigated for 15 N scrambling-prone amino acids, such as Leu, Ile, Tyr, Phe, Thr, Val, and Ala. The level of isotope scrambling was substantially lower in 13 Cα and 13 C side-chain labeling than in 15 N labeling. We utilized this reduced scrambling-prone character of 13 C as a simple and efficient method for amino acid selective 13 C labeling using an Escherichia coli cold-shock expression system and high-cell density fermentation. Using this method, the 13 C labeling efficiency was >80% for Leu and Ile, ∼60% for Tyr and Phe, ∼50% for Thr, ∼40% for Val, and 30-40% for Ala. 1 H- 15 N heteronuclear single-quantum coherence signals of the 15 N scrambling-prone amino acid were also easily filtered using 15 N-{ 13 Cα} spin-echo difference experiments. Our method could be applied to the assignment of the 55 kDa protein.

Dark state polarizing a nuclear spin in the vicinity of a nitrogen-vacancy center

NASA Astrophysics Data System (ADS)

Wang, Yang-Yang; Qiu, Jing; Chu, Ying-Qi; Zhang, Mei; Cai, Jianming; Ai, Qing; Deng, Fu-Guo

2018-04-01

The nuclear spin in the vicinity of a nitrogen-vacancy (NV) center possesses long coherence time and convenient manipulation assisted by the strong hyperfine interaction with the NV center. It is suggested for the subsequent quantum information storage and processing after appropriate initialization. However, current experimental schemes are either sensitive to the inclination and magnitude of the magnetic field or require thousands of repetitions to achieve successful realization. Here, we propose a method to polarize a 13C nuclear spin in the vicinity of an NV center via a dark state. We demonstrate theoretically and numerically that it is robust to polarize various nuclear spins with different hyperfine couplings and noise strengths.

Spectrally edited 2D 13Csbnd 13C NMR spectra without diagonal ridge for characterizing 13C-enriched low-temperature carbon materials

NASA Astrophysics Data System (ADS)

Johnson, Robert L.; Anderson, Jason M.; Shanks, Brent H.; Fang, Xiaowen; Hong, Mei; Schmidt-Rohr, Klaus

2013-09-01

Two robust combinations of spectral editing techniques with 2D 13Csbnd 13C NMR have been developed for characterizing the aromatic components of 13C-enriched low-temperature carbon materials. One method (exchange with protonated and nonprotonated spectral editing, EXPANSE) selects cross peaks of protonated and nearby nonprotonated carbons, while the other technique, dipolar-dephased double-quantum/single-quantum (DQ/SQ) NMR, selects signals of bonded nonprotonated carbons. Both spectra are free of a diagonal ridge, which has many advantages: Cross peaks on the diagonal or of small intensity can be detected, and residual spinning sidebands or truncation artifacts associated with the diagonal ridge are avoided. In the DQ/SQ experiment, dipolar dephasing of the double-quantum coherence removes protonated-carbon signals; this approach also eliminates the need for high-power proton decoupling. The initial magnetization is generated with minimal fluctuation by combining direct polarization, cross polarization, and equilibration by 13C spin diffusion. The dipolar dephased DQ/SQ spectrum shows signals from all linkages between aromatic rings, including a distinctive peak from polycondensed aromatics. In EXPANSE NMR, signals of protonated carbons are selected in the first spectral dimension by short cross polarization combined with dipolar dephasing difference. This removes ambiguities of peak assignment to overlapping signals of nonprotonated and protonated aromatic carbons, e.g. near 125 ppm. Spin diffusion is enhanced by dipolar-assisted rotational resonance. Before detection, Csbnd H dipolar dephasing by gated decoupling is applied, which selects signals of nonprotonated carbons. Thus, only cross peaks due to magnetization originating from protonated C and ending on nearby nonprotonated C are retained. Combined with the chemical shifts deduced from the cross-peak position, this double spectral editing defines the bonding environment of aromatic, COO, and Cdbnd O carbons

Analysis of the transient response of nuclear spins in GaAs with/without nuclear magnetic resonance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rasly, Mahmoud; Lin, Zhichao; Yamamoto, Masafumi

As an alternative to studying the steady-state responses of nuclear spins in solid state systems, working within a transient-state framework can reveal interesting phenomena. The response of nuclear spins in GaAs to a changing magnetic field was analyzed based on the time evolution of nuclear spin temperature. Simulation results well reproduced our experimental results for the transient oblique Hanle signals observed in an all-electrical spin injection device. The analysis showed that the so called dynamic nuclear polarization can be treated as a cooling tool for the nuclear spins: It works as a provider to exchange spin angular momentum between polarizedmore » electron spins and nuclear spins through the hyperfine interaction, leading to an increase in the nuclear polarization. In addition, a time-delay of the nuclear spin temperature with a fast sweep of the external magnetic field produces a possible transient state for the nuclear spin polarization. On the other hand, the nuclear magnetic resonance acts as a heating tool for a nuclear spin system. This causes the nuclear spin temperature to jump to infinity: i.e., the average nuclear spins along with the nuclear field vanish at resonant fields of {sup 75}As, {sup 69}Ga and {sup 71}Ga, showing an interesting step-dip structure in the oblique Hanle signals. These analyses provide a quantitative understanding of nuclear spin dynamics in semiconductors for application in future computation processing.« less

All-electrical production of spin-polarized currents in carbon nanotubes: Rashba spin-orbit interaction

NASA Astrophysics Data System (ADS)

Santos, Hernán; Latgé, A.; Alvarellos, J. E.; Chico, Leonor

2016-04-01

We study the effect of the Rashba spin-orbit interaction in the quantum transport of carbon nanotubes with arbitrary chiralities. For certain spin directions, we find a strong spin-polarized electrical current that depends on the diameter of the tube, the length of the Rashba region, and on the tube chirality. Predictions for the spin-dependent conductances are presented for different families of achiral and chiral tubes. We have found that different symmetries acting on spatial and spin variables have to be considered in order to explain the relations between spin-resolved conductances in carbon nanotubes. These symmetries are more general than those employed in planar graphene systems. Our results indicate the possibility of having stable spin-polarized electrical currents in absence of external magnetic fields or magnetic impurities in carbon nanotubes.

Non-flipping 13C spins near an NV center in diamond: hyperfine and spatial characteristics by density functional theory simulation of the C510[NV]H252 cluster

NASA Astrophysics Data System (ADS)

Nizovtsev, A. P.; Kilin, S. Ya; Pushkarchuk, A. L.; Pushkarchuk, V. A.; Kuten, S. A.; Zhikol, O. A.; Schmitt, S.; Unden, T.; Jelezko, F.

2018-02-01

Single NV centers in diamond coupled by hyperfine interaction (hfi) to neighboring 13C nuclear spins are now widely used in emerging quantum technologies as elements of quantum memory adjusted to a nitrogen-vacancy (NV) center electron spin qubit. For nuclear spins with low flip-flop rate, single shot readout was demonstrated under ambient conditions. Here we report on a systematic search for such stable NV-13C systems using density functional theory to simulate the hfi and spatial characteristics of all possible NV-13C complexes in the H-terminated cluster C510[NV]-H252 hosting the NV center. Along with the expected stable ‘NV-axial-13C’ systems wherein the 13C nuclear spin is located on the NV axis, we found for the first time new families of positions for the 13C nuclear spin exhibiting negligible hfi-induced flipping rates due to near-symmetric local spin density distribution. Spatially, these positions are located in the diamond bilayer passing through the vacancy of the NV center and being perpendicular to the NV axis. Analysis of available publications showed that, apparently, some of the predicted non-axial near-stable NV-13C systems have already been observed experimentally. A special experiment performed on one of these systems confirmed the prediction made.

The electron-spin--nuclear-spin interaction studied by polarized neutron scattering.

PubMed

Stuhrmann, Heinrich B

2007-11-01

Dynamic nuclear spin polarization (DNP) is mediated by the dipolar interaction of paramagnetic centres with nuclear spins. This process is most likely to occur near paramagnetic centres at an angle close to 45 degrees with respect to the direction of the external magnetic field. The resulting distribution of polarized nuclear spins leads to an anisotropy of the polarized neutron scattering pattern, even with randomly oriented radical molecules. The corresponding cross section of polarized coherent neutron scattering in terms of a multipole expansion is derived for radical molecules in solution. An application using data of time-resolved polarized neutron scattering from an organic chromium(V) molecule is tested.

A facile synthesis and carbon-13 nuclear magnetic resonance spectral properties of 7-ketocholesteryl benzoate.

PubMed

Parish, E J; Wei, T Y; Livant, P

1987-10-01

This paper presents a modified method of the selective allylic oxidation of cholesteryl benzoate. Pyridinium chlorochromate, in refluxing benzene, has been found to be an effective and convenient reagent for the efficient oxidation of cholesteryl benzoate to 7-ketocholesteryl benzoate in high yield. Also included herein are the carbon-13 nuclear magnetic resonance spectral properties of 7-ketocholesteryl benzoate and cholesteryl benzoate.

Electronic Spin Storage in an Electrically Readable Nuclear Spin Memory with a Lifetime >100 Seconds

NASA Astrophysics Data System (ADS)

McCamey, D. R.; Van Tol, J.; Morley, G. W.; Boehme, C.

2010-12-01

Electron spins are strong candidates with which to implement spintronics because they are both mobile and able to be manipulated. The relatively short lifetimes of electron spins, however, present a problem for the long-term storage of spin information. We demonstrated an ensemble nuclear spin memory in phosphorous-doped silicon, which can be read out electrically and has a lifetime exceeding 100 seconds. The electronic spin information can be mapped onto and stored in the nuclear spin of the phosphorus donors, and the nuclear spins can then be repetitively read out electrically for time periods that exceed the electron spin lifetime. We discuss how this memory can be used in conjunction with other silicon spintronic devices.

Dynamic nuclear polarization assisted spin diffusion for the solid effect case.

PubMed

Hovav, Yonatan; Feintuch, Akiva; Vega, Shimon

2011-02-21

The dynamic nuclear polarization (DNP) process in solids depends on the magnitudes of hyperfine interactions between unpaired electrons and their neighboring (core) nuclei, and on the dipole-dipole interactions between all nuclei in the sample. The polarization enhancement of the bulk nuclei has been typically described in terms of a hyperfine-assisted polarization of a core nucleus by microwave irradiation followed by a dipolar-assisted spin diffusion process in the core-bulk nuclear system. This work presents a theoretical approach for the study of this combined process using a density matrix formalism. In particular, solid effect DNP on a single electron coupled to a nuclear spin system is considered, taking into account the interactions between the spins as well as the main relaxation mechanisms introduced via the electron, nuclear, and cross-relaxation rates. The basic principles of the DNP-assisted spin diffusion mechanism, polarizing the bulk nuclei, are presented, and it is shown that the polarization of the core nuclei and the spin diffusion process should not be treated separately. To emphasize this observation the coherent mechanism driving the pure spin diffusion process is also discussed. In order to demonstrate the effects of the interactions and relaxation mechanisms on the enhancement of the nuclear polarization, model systems of up to ten spins are considered and polarization buildup curves are simulated. A linear chain of spins consisting of a single electron coupled to a core nucleus, which in turn is dipolar coupled to a chain of bulk nuclei, is considered. The interaction and relaxation parameters of this model system were chosen in a way to enable a critical analysis of the polarization enhancement of all nuclei, and are not far from the values of (13)C nuclei in frozen (glassy) organic solutions containing radicals, typically used in DNP at high fields. Results from the simulations are shown, demonstrating the complex dependences of the DNP

Nuclear spin nanomagnet in an optically excited quantum dot.

PubMed

Korenev, V L

2007-12-21

Linearly polarized light tuned slightly below the optical transition of the negatively charged exciton (trion) in a single quantum dot causes the spontaneous nuclear spin polarization (self-polarization) at a level close to 100%. The effective magnetic field of spin-polarized nuclei shifts the optical transition energy close to resonance with photon energy. The resonantly enhanced Overhauser effect sustains the stability of the nuclear self-polarization even in the absence of spin polarization of the quantum dot electron. As a result the optically selected single quantum dot represents a tiny magnet with the ferromagnetic ordering of nuclear spins-the nuclear spin nanomagnet.

Measurement of untruncated nuclear spin interactions via zero- to ultralow-field nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Blanchard, J. W.; Sjolander, T. F.; King, J. P.; Ledbetter, M. P.; Levine, E. H.; Bajaj, V. S.; Budker, D.; Pines, A.

2015-12-01

Zero- to ultralow-field nuclear magnetic resonance (ZULF NMR) provides a new regime for the measurement of nuclear spin-spin interactions free from the effects of large magnetic fields, such as truncation of terms that do not commute with the Zeeman Hamiltonian. One such interaction, the magnetic dipole-dipole coupling, is a valuable source of spatial information in NMR, though many terms are unobservable in high-field NMR, and the coupling averages to zero under isotropic molecular tumbling. Under partial alignment, this information is retained in the form of so-called residual dipolar couplings. We report zero- to ultralow-field NMR measurements of residual dipolar couplings in acetonitrile-2-13C aligned in stretched polyvinyl acetate gels. This permits the investigation of dipolar couplings as a perturbation on the indirect spin-spin J coupling in the absence of an applied magnetic field. As a consequence of working at zero magnetic field, we observe terms of the dipole-dipole coupling Hamiltonian that are invisible in conventional high-field NMR. This technique expands the capabilities of zero- to ultralow-field NMR and has potential applications in precision measurement of subtle physical interactions, chemical analysis, and characterization of local mesoscale structure in materials.

Electron-nuclear coherent spin oscillations probed by spin-dependent recombination

NASA Astrophysics Data System (ADS)

Azaizia, S.; Carrère, H.; Sandoval-Santana, J. C.; Ibarra-Sierra, V. G.; Kalevich, V. K.; Ivchenko, E. L.; Bakaleinikov, L. A.; Marie, X.; Amand, T.; Kunold, A.; Balocchi, A.

2018-04-01

We demonstrate the triggering and detection of coherent electron-nuclear spin oscillations related to the hyperfine interaction in Ga deep paramagnetic centers in GaAsN by band-to-band photoluminescence without an external magnetic field. In contrast to other point defects such as Cr4 + in SiC, Ce3 + in yttrium aluminum garnet crystals, nitrogen-vacancy centers in diamond, and P atoms in silicon, the bound-electron spin in Ga centers is not directly coupled to the electromagnetic field via the spin-orbit interaction. However, this apparent drawback can be turned into an advantage by exploiting the spin-selective capture of conduction band electrons to the Ga centers. On the basis of a pump-probe photoluminescence experiment we measure directly in the temporal domain the hyperfine constant of an electron coupled to a gallium defect in GaAsN by tracing the dynamical behavior of the conduction electron spin-dependent recombination to the defect site. The hyperfine constants and the relative abundance of the nuclei isotopes involved can be determined without the need of an electron spin resonance technique and in the absence of any magnetic field. Information on the nuclear and electron spin relaxation damping parameters can also be estimated from the oscillation amplitude decay and the long-time-delay behavior.

Stabilization of the electron-nuclear spin orientation in quantum dots by the nuclear quadrupole interaction.

PubMed

Dzhioev, R I; Korenev, V L

2007-07-20

The nuclear quadrupole interaction eliminates the restrictions imposed by hyperfine interaction on the spin coherence of an electron and nuclei in a quantum dot. The strain-induced nuclear quadrupole interaction suppresses the nuclear spin flip and makes possible the zero-field dynamic nuclear polarization in self-organized InP/InGaP quantum dots. The direction of the effective nuclear magnetic field is fixed in space, thus quenching the magnetic depolarization of the electron spin in the quantum dot. The quadrupole interaction suppresses the zero-field electron spin decoherence also for the case of nonpolarized nuclei. These results provide a new vision of the role of the nuclear quadrupole interaction in nanostructures: it elongates the spin memory of the electron-nuclear system.

Stabilization of the Electron-Nuclear Spin Orientation in Quantum Dots by the Nuclear Quadrupole Interaction

NASA Astrophysics Data System (ADS)

Dzhioev, R. I.; Korenev, V. L.

2007-07-01

The nuclear quadrupole interaction eliminates the restrictions imposed by hyperfine interaction on the spin coherence of an electron and nuclei in a quantum dot. The strain-induced nuclear quadrupole interaction suppresses the nuclear spin flip and makes possible the zero-field dynamic nuclear polarization in self-organized InP/InGaP quantum dots. The direction of the effective nuclear magnetic field is fixed in space, thus quenching the magnetic depolarization of the electron spin in the quantum dot. The quadrupole interaction suppresses the zero-field electron spin decoherence also for the case of nonpolarized nuclei. These results provide a new vision of the role of the nuclear quadrupole interaction in nanostructures: it elongates the spin memory of the electron-nuclear system.

The effect of 13C enrichment in the glassing matrix on dynamic nuclear polarization of [1-13C]pyruvate

NASA Astrophysics Data System (ADS)

Lumata, Lloyd; Kovacs, Zoltan; Malloy, Craig; Sherry, A. Dean; Merritt, Matthew

2011-03-01

Dimethyl sulfoxide (DMSO) can effectively form a glassy matrix necessary for dynamic nuclear polarization (DNP) experiments. We tested the effects of 13C enrichment in DMSO on DNP of [1-13C]pyruvate doped with trityl radical OX063Me. We found that the polarization build-up time τ of pyruvate in 13C-labeled DMSO glassing solution is twice as fast as the unenriched DMSO while the nuclear magnetic resonance enhancement was unchanged. This indicates that 13C-13C spin diffusion is a limiting factor in the kinetics of DNP in this system, but it has a minimal effect on the absolute value of polarization achievable for the target.

Nuclear Spin Nanomagnet in an Optically Excited Quantum Dot

NASA Astrophysics Data System (ADS)

Korenev, V. L.

2007-12-01

Linearly polarized light tuned slightly below the optical transition of the negatively charged exciton (trion) in a single quantum dot causes the spontaneous nuclear spin polarization (self-polarization) at a level close to 100%. The effective magnetic field of spin-polarized nuclei shifts the optical transition energy close to resonance with photon energy. The resonantly enhanced Overhauser effect sustains the stability of the nuclear self-polarization even in the absence of spin polarization of the quantum dot electron. As a result the optically selected single quantum dot represents a tiny magnet with the ferromagnetic ordering of nuclear spins—the nuclear spin nanomagnet.

Quantum many-body theory for electron spin decoherence in nanoscale nuclear spin baths.

PubMed

Yang, Wen; Ma, Wen-Long; Liu, Ren-Bao

2017-01-01

Decoherence of electron spins in nanoscale systems is important to quantum technologies such as quantum information processing and magnetometry. It is also an ideal model problem for studying the crossover between quantum and classical phenomena. At low temperatures or in light-element materials where the spin-orbit coupling is weak, the phonon scattering in nanostructures is less important and the fluctuations of nuclear spins become the dominant decoherence mechanism for electron spins. Since the 1950s, semi-classical noise theories have been developed for understanding electron spin decoherence. In spin-based solid-state quantum technologies, the relevant systems are in the nanometer scale and nuclear spin baths are quantum objects which require a quantum description. Recently, quantum pictures have been established to understand the decoherence and quantum many-body theories have been developed to quantitatively describe this phenomenon. Anomalous quantum effects have been predicted and some have been experimentally confirmed. A systematically truncated cluster-correlation expansion theory has been developed to account for the many-body correlations in nanoscale nuclear spin baths that are built up during electron spin decoherence. The theory has successfully predicted and explained a number of experimental results in a wide range of physical systems. In this review, we will cover this recent progress. The limitations of the present quantum many-body theories and possible directions for future development will also be discussed.

NOTE The effect of 13C enrichment in the glassing matrix on dynamic nuclear polarization of [1-13C]pyruvate

NASA Astrophysics Data System (ADS)

Lumata, Lloyd; Kovacs, Zoltan; Malloy, Craig; Sherry, A. Dean; Merritt, Matthew

2011-03-01

Dimethyl sulfoxide (DMSO) can effectively form a glassy matrix necessary for dynamic nuclear polarization (DNP) experiments. We tested the effects of 13C enrichment in DMSO on DNP of [1-13C]pyruvate doped with trityl radical OX063Me. We found that the polarization build-up time τ of pyruvate in 13C-labeled DMSO glassing solution is twice as fast as the unenriched DMSO while the nuclear magnetic resonance enhancement was unchanged. This indicates that 13C-13C spin diffusion is a limiting factor in the kinetics of DNP in this system, but it has a minimal effect on the absolute value of polarization achievable for the target.

Spin Transport in Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Schoenenberger, Christian

2005-03-01

We report on spin transport in carbon nanotubes. First, spin injection in arc-discharge grown multi-walled carbon nanotubes (MWNTs) is achieved by using a ferromagnetic PdNi alloy as contact material. The two contacts, i.e. source and drain, have different shape rendering different magnetic switching fields. Typical two-terminal resistances are in the range of 5-100 kOhm. We find a tunneling magneto resistance (TMR) signal amounting to 2.5-3%. Secondly, we explore the TMR signal as a function of temperature T, source-drain voltage Vsd, and gate voltage Vg. As expected the TMR signal decays with T and Vsd. Remarkably, however, we find a sign change in the spin signal (the TMR signal) as a function of both Vsd and Vg. This work has been done in collaboration with: S. Sahoo and T. Kontos (Univ. of Basel), C. Sürgers (Univ. of Karlsruhe), and L. Forro (EPFL Lausanne).

Stimulated Raman adiabatic control of a nuclear spin in diamond

NASA Astrophysics Data System (ADS)

Coto, Raul; Jacques, Vincent; Hétet, Gabriel; Maze, Jerónimo R.

2017-08-01

Coherent manipulation of nuclear spins is a highly desirable tool for both quantum metrology and quantum computation. However, most of the current techniques to control nuclear spins lack fast speed, impairing their robustness against decoherence. Here, based on stimulated Raman adiabatic passage, and its modification including shortcuts to adiabaticity, we present a fast protocol for the coherent manipulation of nuclear spins. Our proposed Λ scheme is implemented in the microwave domain and its excited-state relaxation can be optically controlled through an external laser excitation. These features allow for the initialization of a nuclear spin starting from a thermal state. Moreover we show how to implement Raman control for performing Ramsey spectroscopy to measure the dynamical and geometric phases acquired by nuclear spins.

13C nuclear magnetic resonance and gas chromatography-mass spectrometry studies of carbon metabolism in the actinomycin D producer Streptomyces parvulus by use of 13C-labeled precursors.

PubMed Central

Inbar, L; Lapidot, A

1991-01-01

Fructose and glutamate metabolism was monitored in cell suspensions of streptomyces parvulus by 13C nuclear magnetic resonance. The experiments were performed for cells grown with various 13C sources in a growth medium containing D-[U-13C]fructose, L-[13C]glutamate, or L-[U-13C]aspartate and with nonlabeled precursors to compare intracellular pools in S. parvulus cells at different periods of the cell life cycle. The transport of fructose into the cells was biphasic in nature; during rapid transport, mannitol, fructose, and glucose 6-phosphate were accumulated intracellularly, whereas during the passive diffusion of fructose, the intracellular carbohydrate pool comprised mainly trehalose (1,1'-alpha-alpha-D-glucose). The regulation of fructokinase activity by the intracellular intermediates may play an important role in fructose catabolism in S. parvulus. Transaldolase activity in S. parvulus was determined from the 13C nuclear magnetic resonance labeling pattern of trehalose carbons obtained from cells grown in medium containing either L-[U-13C]aspartate or L-[U-13C]glutamate. Only carbons 4, 5, and 6 of the disaccharide were labeled. Isotopomer analysis of the trehalose carbons led us to conclude that the flux through the reverse glycolytic pathway, condensation of glyceraldehyde 3-phosphate with dihydroxyacetone phosphate, makes at best a minor contribution to the 13C-labeled glucose units observed in trehalose. The pentose pathway and transaldolase activity can explain the labeling pattern of 4,5,6-13C3 of trehalose. Moreover, the transfer of the 13C label of L-[U-13C]aspartate into the different isotopomers of trehalose C4, C5, and C6 by the transaldolase activity allowed us to calculate the relative fluxes from oxaloacetate via gluconeogenesis and through the tricarboxylic acid cycle. The ratio of the two fluxes is approximately 1. However, the main carbon source for trehalose synthesis in S. parvulus is fructose and not glutamate or aspartate. The 13C

Nuclear-Spin Gyroscope Based on an Atomic Co-Magnetometer

NASA Technical Reports Server (NTRS)

Romalis, Michael; Komack, Tom; Ghost, Rajat

2008-01-01

An experimental nuclear-spin gyroscope is based on an alkali-metal/noblegas co-magnetometer, which automatically cancels the effects of magnetic fields. Whereas the performances of prior nuclear-spin gyroscopes are limited by sensitivity to magnetic fields, this gyroscope is insensitive to magnetic fields and to other external perturbations. In addition, relative to prior nuclear-spin gyroscopes, this one exhibits greater sensitivity to rotation. There is commercial interest in development of small, highly sensitive gyroscopes. The present experimental device could be a prototype for development of nuclear spin gyroscopes suitable for navigation. In comparison with fiber-optic gyroscopes, these gyroscopes would draw less power and would be smaller, lighter, more sensitive, and less costly.

Nonlocal Nuclear Spin Quieting in Quantum Dot Molecules: Optically Induced Extended Two-Electron Spin Coherence Time.

PubMed

Chow, Colin M; Ross, Aaron M; Kim, Danny; Gammon, Daniel; Bracker, Allan S; Sham, L J; Steel, Duncan G

2016-08-12

We demonstrate the extension of coherence between all four two-electron spin ground states of an InAs quantum dot molecule (QDM) via nonlocal suppression of nuclear spin fluctuations in two vertically stacked quantum dots (QDs), while optically addressing only the top QD transitions. Long coherence times are revealed through dark-state spectroscopy as resulting from nuclear spin locking mediated by the exchange interaction between the QDs. Line shape analysis provides the first measurement of the quieting of the Overhauser field distribution correlating with reduced nuclear spin fluctuations.

Nonlocal Nuclear Spin Quieting in Quantum Dot Molecules: Optically Induced Extended Two-Electron Spin Coherence Time

NASA Astrophysics Data System (ADS)

Chow, Colin M.; Ross, Aaron M.; Kim, Danny; Gammon, Daniel; Bracker, Allan S.; Sham, L. J.; Steel, Duncan G.

2016-08-01

We demonstrate the extension of coherence between all four two-electron spin ground states of an InAs quantum dot molecule (QDM) via nonlocal suppression of nuclear spin fluctuations in two vertically stacked quantum dots (QDs), while optically addressing only the top QD transitions. Long coherence times are revealed through dark-state spectroscopy as resulting from nuclear spin locking mediated by the exchange interaction between the QDs. Line shape analysis provides the first measurement of the quieting of the Overhauser field distribution correlating with reduced nuclear spin fluctuations.

Inhomogeneous nuclear spin polarization induced by helicity-modulated optical excitation of fluorine-bound electron spins in ZnSe

NASA Astrophysics Data System (ADS)

Heisterkamp, F.; Greilich, A.; Zhukov, E. A.; Kirstein, E.; Kazimierczuk, T.; Korenev, V. L.; Yugova, I. A.; Yakovlev, D. R.; Pawlis, A.; Bayer, M.

2015-12-01

Optically induced nuclear spin polarization in a fluorine-doped ZnSe epilayer is studied by time-resolved Kerr rotation using resonant excitation of donor-bound excitons. Excitation with helicity-modulated laser pulses results in a transverse nuclear spin polarization, which is detected as a change of the Larmor precession frequency of the donor-bound electron spins. The frequency shift in dependence on the transverse magnetic field exhibits a pronounced dispersion-like shape with resonances at the fields of nuclear magnetic resonance of the constituent zinc and selenium isotopes. It is studied as a function of external parameters, particularly of constant and radio frequency external magnetic fields. The width of the resonance and its shape indicate a strong spatial inhomogeneity of the nuclear spin polarization in the vicinity of a fluorine donor. A mechanism of optically induced nuclear spin polarization is suggested based on the concept of resonant nuclear spin cooling driven by the inhomogeneous Knight field of the donor-bound electron.

Electron Spin Dephasing and Decoherence by Interaction with Nuclear Spins in Self-Assembled Quantum Dots

NASA Technical Reports Server (NTRS)

Lee, Seungwon; vonAllmen, Paul; Oyafuso, Fabiano; Klimeck, Gerhard; Whale, K. Birgitta

2004-01-01

Electron spin dephasing and decoherence by its interaction with nuclear spins in self-assembled quantum dots are investigated in the framework of the empirical tight-binding model. Electron spin dephasing in an ensemble of dots is induced by the inhomogeneous precession frequencies of the electron among dots, while electron spin decoherence in a single dot arises from the inhomogeneous precession frequencies of nuclear spins in the dot. For In(x)Ga(1-x) As self-assembled dots containing 30000 nuclei, the dephasing and decoherence times are predicted to be on the order of 100 ps and 1 (micro)s.

Hyperpolarized carbon-13 magnetic resonance spectroscopic imaging: a clinical tool for studying tumour metabolism.

PubMed

Zaccagna, Fulvio; Grist, James T; Deen, Surrin S; Woitek, Ramona; Lechermann, Laura Mt; McLean, Mary A; Basu, Bristi; Gallagher, Ferdia A

2018-05-01

Glucose metabolism in tumours is reprogrammed away from oxidative metabolism, even in the presence of oxygen. Non-invasive imaging techniques can probe these alterations in cancer metabolism providing tools to detect tumours and their response to therapy. Although Positron Emission Tomography with ( 18 F)2-fluoro-2-deoxy-D-glucose ( 18 F-FDG PET) is an established clinical tool to probe cancer metabolism, it has poor spatial resolution and soft tissue contrast, utilizes ionizing radiation and only probes glucose uptake and phosphorylation and not further downstream metabolism. Magnetic Resonance Spectroscopy (MRS) has the capability to non-invasively detect and distinguish molecules within tissue but has low sensitivity and can only detect selected nuclei. Dynamic Nuclear Polarization (DNP) is a technique which greatly increases the signal-to-noise ratio (SNR) achieved with MR by significantly increasing nuclear spin polarization and this method has now been translated into human imaging. This review provides a brief overview of this process, also termed Hyperpolarized Carbon-13 Magnetic Resonance Spectroscopic Imaging (HP 13 C-MRSI), its applications in preclinical imaging, an outline of the current human trials that are ongoing, as well as future potential applications in oncology.

Phenomenological study of decoherence in solid-state spin qubits due to nuclear spin diffusion

NASA Astrophysics Data System (ADS)

Biercuk, Michael J.; Bluhm, Hendrik

2011-06-01

We present a study of the prospects for coherence preservation in solid-state spin qubits using dynamical decoupling protocols. Recent experiments have provided the first demonstrations of multipulse dynamical decoupling sequences in this qubit system, but quantitative analyses of potential coherence improvements have been hampered by a lack of concrete knowledge of the relevant noise processes. We present calculations of qubit coherence under the application of arbitrary dynamical decoupling pulse sequences based on an experimentally validated semiclassical model. This phenomenological approach bundles the details of underlying noise processes into a single experimentally relevant noise power spectral density. Our results show that the dominant features of experimental measurements in a two-electron singlet-triplet spin qubit can be replicated using a 1/ω2 noise power spectrum associated with nuclear spin flips in the host material. Beginning with this validation, we address the effects of nuclear programming, high-frequency nuclear spin dynamics, and other high-frequency classical noise sources, with conjectures supported by physical arguments and microscopic calculations where relevant. Our results provide expected performance bounds and identify diagnostic metrics that can be measured experimentally in order to better elucidate the underlying nuclear spin dynamics.

13C NMR spectroscopy of the insoluble carbon of carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Cronin, J. R.; Pizzarello, S.; Frye, J. S.

1987-01-01

13C NMR spectra have been obtained of the insoluble carbon residues resulting from HF-digestion of three carbonaceous chondrites, Orgueil (C1), Murchison (CM2), and Allende (CV3). Spectra obtained using the cross polarization magic-angle spinning technique show two major features attributable respectively to carbon in aliphatic/olefinic structures. The spectrum obtained from the Allende sample was weak, presumably as a consequence of its low hydrogen content. Single pulse excitation spectra, which do not depend on 1H-13C polarization transfer for signal enhancement were also obtained. These spectra, which may be more representative of the total carbon in the meteorite samples, indicate a greater content of carbon in aromatic/olefinic structures. These results suggest that extensive polycyclic aromatic sheets are important structural features of the insoluble carbon of all three meteorites. The Orgueil and Murchison materials contain additional hydrogenated aromatic/olefinic and aliphatic groups.

High-fidelity readout and control of a nuclear spin qubit in silicon.

PubMed

Pla, Jarryd J; Tan, Kuan Y; Dehollain, Juan P; Lim, Wee H; Morton, John J L; Zwanenburg, Floris A; Jamieson, David N; Dzurak, Andrew S; Morello, Andrea

2013-04-18

Detection of nuclear spin precession is critical for a wide range of scientific techniques that have applications in diverse fields including analytical chemistry, materials science, medicine and biology. Fundamentally, it is possible because of the extreme isolation of nuclear spins from their environment. This isolation also makes single nuclear spins desirable for quantum-information processing, as shown by pioneering studies on nitrogen-vacancy centres in diamond. The nuclear spin of a (31)P donor in silicon is very promising as a quantum bit: bulk measurements indicate that it has excellent coherence times and silicon is the dominant material in the microelectronics industry. Here we demonstrate electrical detection and coherent manipulation of a single (31)P nuclear spin qubit with sufficiently high fidelities for fault-tolerant quantum computing. By integrating single-shot readout of the electron spin with on-chip electron spin resonance, we demonstrate quantum non-demolition and electrical single-shot readout of the nuclear spin with a readout fidelity higher than 99.8 percent-the highest so far reported for any solid-state qubit. The single nuclear spin is then operated as a qubit by applying coherent radio-frequency pulses. For an ionized (31)P donor, we find a nuclear spin coherence time of 60 milliseconds and a one-qubit gate control fidelity exceeding 98 percent. These results demonstrate that the dominant technology of modern electronics can be adapted to host a complete electrical measurement and control platform for nuclear-spin-based quantum-information processing.

All-electric control of donor nuclear spin qubits in silicon

NASA Astrophysics Data System (ADS)

Sigillito, Anthony J.; Tyryshkin, Alexei M.; Schenkel, Thomas; Houck, Andrew A.; Lyon, Stephen A.

2017-10-01

The electronic and nuclear spin degrees of freedom of donor impurities in silicon form ultra-coherent two-level systems that are potentially useful for applications in quantum information and are intrinsically compatible with industrial semiconductor processing. However, because of their smaller gyromagnetic ratios, nuclear spins are more difficult to manipulate than electron spins and are often considered too slow for quantum information processing. Moreover, although alternating current magnetic fields are the most natural choice to drive spin transitions and implement quantum gates, they are difficult to confine spatially to the level of a single donor, thus requiring alternative approaches. In recent years, schemes for all-electrical control of donor spin qubits have been proposed but no experimental demonstrations have been reported yet. Here, we demonstrate a scalable all-electric method for controlling neutral 31P and 75As donor nuclear spins in silicon. Using coplanar photonic bandgap resonators, we drive Rabi oscillations on nuclear spins exclusively using electric fields by employing the donor-bound electron as a quantum transducer, much in the spirit of recent works with single-molecule magnets. The electric field confinement leads to major advantages such as low power requirements, higher qubit densities and faster gate times. Additionally, this approach makes it possible to drive nuclear spin qubits either at their resonance frequency or at its first subharmonic, thus reducing device bandwidth requirements. Double quantum transitions can be driven as well, providing easy access to the full computational manifold of our system and making it convenient to implement nuclear spin-based qudits using 75As donors.

Decoherence and fluctuation dynamics of the quantum dot nuclear spin bath probed by nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Chekhovich, Evgeny A.

2017-06-01

Dynamics of nuclear spin decoherence and nuclear spin flip-flops in self-assembled InGaAs/GaAs quantum dots are studied experimentally using optically detected nuclear magnetic resonance (NMR). Nuclear spin-echo decay times are found to be in the range 1-4 ms. This is a factor of ~3 longer than in strain-free GaAs/AlGaAs structures and is shown to result from strain-induced quadrupolar effects that suppress nuclear spin flip-flops. The correlation times of the flip-flops are examined using a novel frequency-comb NMR technique and are found to exceed 1 s, a factor of ~1000 longer than in strain-free structures. These findings complement recent studies of electron spin coherence and reveal the paradoxical dual role of the quadrupolar effects in self-assembled quantum dots: large increase of the nuclear spin bath coherence and at the same time significant reduction of the electron spin-qubit coherence. Approaches to increasing electron spin coherence are discussed. In particular the nanohole filled GaAs/AlGaAs quantum dots are an attractive option: while their optical quality matches the self-assembled dots the quadrupolar effects measured in NMR spectra are a factor of 1000 smaller.

Full four-component relativistic calculations of the one-bond 77Se-13C spin-spin coupling constants in the series of selenium heterocycles and their parent open-chain selenides.

PubMed

Rusakov, Yury Yu; Rusakova, Irina L; Krivdin, Leonid B

2014-05-01

Four-component relativistic calculations of (77)Se-(13)C spin-spin coupling constants have been performed in the series of selenium heterocycles and their parent open-chain selenides. It has been found that relativistic effects play an essential role in the selenium-carbon coupling mechanism and could result in a contribution of as much as 15-25% of the total values of the one-bond selenium-carbon spin-spin coupling constants. In the overall contribution of the relativistic effects to the total values of (1)J(Se,C), the scalar relativistic corrections (negative in sign) by far dominate over the spin-orbit ones (positive in sign), the latter being of less than 5%, as compared to the former (ca 20%). A combination of nonrelativistic second-order polarization propagator approach (CC2) with the four-component relativistic density functional theory scheme is recommended as a versatile tool for the calculation of (1)J(Se,C). Solvent effects in the values of (1)J(Se,C) calculated within the polarizable continuum model for the solvents with different dielectric constants (ε 2.2-78.4) are next to negligible decreasing negative (1)J(Se,C) in absolute value by only about 1 Hz. The use of the locally dense basis set approach applied herewith for the calculation of (77)Se-(13)C spin-spin coupling constants is fully justified resulting in a dramatic decrease in computational cost with only 0.1-0.2-Hz loss of accuracy. Copyright © 2014 John Wiley & Sons, Ltd.

Notch filtering the nuclear environment of a spin qubit.

PubMed

Malinowski, Filip K; Martins, Frederico; Nissen, Peter D; Barnes, Edwin; Cywiński, Łukasz; Rudner, Mark S; Fallahi, Saeed; Gardner, Geoffrey C; Manfra, Michael J; Marcus, Charles M; Kuemmeth, Ferdinand

2017-01-01

Electron spins in gate-defined quantum dots provide a promising platform for quantum computation. In particular, spin-based quantum computing in gallium arsenide takes advantage of the high quality of semiconducting materials, reliability in fabricating arrays of quantum dots and accurate qubit operations. However, the effective magnetic noise arising from the hyperfine interaction with uncontrolled nuclear spins in the host lattice constitutes a major source of decoherence. Low-frequency nuclear noise, responsible for fast (10 ns) inhomogeneous dephasing, can be removed by echo techniques. High-frequency nuclear noise, recently studied via echo revivals, occurs in narrow-frequency bands related to differences in Larmor precession of the three isotopes 69 Ga, 71 Ga and 75 As (refs 15,16,17). Here, we show that both low- and high-frequency nuclear noise can be filtered by appropriate dynamical decoupling sequences, resulting in a substantial enhancement of spin qubit coherence times. Using nuclear notch filtering, we demonstrate a spin coherence time (T 2 ) of 0.87 ms, five orders of magnitude longer than typical exchange gate times, and exceeding the longest coherence times reported to date in Si/SiGe gate-defined quantum dots.

Influence of 13C isotopic labeling location of 13C DNP of acetate using TEMPO free radical

NASA Astrophysics Data System (ADS)

Parish, Christopher; Niedbalski, Peter; Lumata, Lloyd

2015-03-01

Dynamic nuclear polarization (DNP) via the dissolution method enhances the liquid-state magnetic resonance (NMR or MRI) signals of insensitive nuclear spins by at least 10,000-fold. The basis for all these signal enhancements at room temperature is the polarization transfer from the electrons to nuclear spins at cryogenic temperature and high magnetic field. In this work, we have studied the influence of the location of 13C isotopic labeling on the DNP of sodium acetate at 3.35 T and 1.4 K using a wide ESR linewidth free radical 4-oxo-TEMPO. The carbonyl [1-13C]acetate spins produced a polarization level that is almost twice that of the methyl [2-13C]acetate spins. On the other hand, the polarization of the methyl 13C spins doubled to reach the level of [1-13C]acetate when the methyl group was deuterated. Meanwhile, the solid-state nuclear relaxation of these samples are the same and do not correlate with the polarization levels. These behavior implies that the nuclear relaxation for these samples is dominated by the contribution from the free radicals and the polarization levels can be explained by a thermodynamic picture of DNP.

Analyses of cocondensation of melamine and urea through carbon 13 enriched formaldehyde with carbon 13 nuclear magnetic resonance spectroscopy

Treesearch

Tomita Bunchiro; Chung-Yun Hse

1995-01-01

The urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, and melamine-urea-formaldehyde (MUF) cocondensed resins were synthesized using the labeling method with 13C enriched formaldehyde unde neutral conditions and their 13C-NMR (nuclear magnetic resonance) spectra were analyzed. The remarkable down-field...

Dephasing due to Nuclear Spins in Large-Amplitude Electric Dipole Spin Resonance.

PubMed

Chesi, Stefano; Yang, Li-Ping; Loss, Daniel

2016-02-12

We analyze effects of the hyperfine interaction on electric dipole spin resonance when the amplitude of the quantum-dot motion becomes comparable or larger than the quantum dot's size. Away from the well-known small-drive regime, the important role played by transverse nuclear fluctuations leads to a Gaussian decay with characteristic dependence on drive strength and detuning. A characterization of spin-flip gate fidelity, in the presence of such additional drive-dependent dephasing, shows that vanishingly small errors can still be achieved at sufficiently large amplitudes. Based on our theory, we analyze recent electric dipole spin resonance experiments relying on spin-orbit interactions or the slanting field of a micromagnet. We find that such experiments are already in a regime with significant effects of transverse nuclear fluctuations and the form of decay of the Rabi oscillations can be reproduced well by our theory.

Analysis on cocondensation of melamine and urea through carbon 13 enriched formaldehyde with carbon 13 nuclear magnetic resonance spectroscopy

Treesearch

Bunichiro Tomita; Chung-Yun Hse

1995-01-01

The urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, and melamine-urea-formaldehyde (MUF) cocondensed resins were synthesized using the labeling method of 13C enriched formaldehyde udner neutral conditions and their 13C-NMR (nuclear magnetic resonance) spectra were analyzed. The remarkable down-field shifts...

A quantum spin-probe molecular microscope

NASA Astrophysics Data System (ADS)

Perunicic, V. S.; Hill, C. D.; Hall, L. T.; Hollenberg, L. C. L.

2016-10-01

Imaging the atomic structure of a single biomolecule is an important challenge in the physical biosciences. Whilst existing techniques all rely on averaging over large ensembles of molecules, the single-molecule realm remains unsolved. Here we present a protocol for 3D magnetic resonance imaging of a single molecule using a quantum spin probe acting simultaneously as the magnetic resonance sensor and source of magnetic field gradient. Signals corresponding to specific regions of the molecule's nuclear spin density are encoded on the quantum state of the probe, which is used to produce a 3D image of the molecular structure. Quantum simulations of the protocol applied to the rapamycin molecule (C51H79NO13) show that the hydrogen and carbon substructure can be imaged at the angstrom level using current spin-probe technology. With prospects for scaling to large molecules and/or fast dynamic conformation mapping using spin labels, this method provides a realistic pathway for single-molecule microscopy.

Magnetic field sensors using 13-spin cat states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simmons, Stephanie; Karlen, Steven D.; Jones, Jonathan A.

2010-08-15

Measurement devices could benefit from entangled correlations to yield a measurement sensitivity approaching the physical Heisenberg limit. Building upon previous magnetometric work using pseudoentangled spin states in solution-state NMR, we present two conceptual advancements to better prepare and interpret the pseudoentanglement resource. We apply these to a 13-spin cat state to measure the local magnetic field with a 12.2 sensitivity increase over an equivalent number of isolated spins.

Atomic-Scale Nuclear Spin Imaging Using Quantum-Assisted Sensors in Diamond

NASA Astrophysics Data System (ADS)

Ajoy, A.; Bissbort, U.; Lukin, M. D.; Walsworth, R. L.; Cappellaro, P.

2015-01-01

Nuclear spin imaging at the atomic level is essential for the understanding of fundamental biological phenomena and for applications such as drug discovery. The advent of novel nanoscale sensors promises to achieve the long-standing goal of single-protein, high spatial-resolution structure determination under ambient conditions. In particular, quantum sensors based on the spin-dependent photoluminescence of nitrogen-vacancy (NV) centers in diamond have recently been used to detect nanoscale ensembles of external nuclear spins. While NV sensitivity is approaching single-spin levels, extracting relevant information from a very complex structure is a further challenge since it requires not only the ability to sense the magnetic field of an isolated nuclear spin but also to achieve atomic-scale spatial resolution. Here, we propose a method that, by exploiting the coupling of the NV center to an intrinsic quantum memory associated with the nitrogen nuclear spin, can reach a tenfold improvement in spatial resolution, down to atomic scales. The spatial resolution enhancement is achieved through coherent control of the sensor spin, which creates a dynamic frequency filter selecting only a few nuclear spins at a time. We propose and analyze a protocol that would allow not only sensing individual spins in a complex biomolecule, but also unraveling couplings among them, thus elucidating local characteristics of the molecule structure.

Excited-State Spin Manipulation and Intrinsic Nuclear Spin Memory using Single Nitrogen-Vacancy Centers in Diamond

NASA Astrophysics Data System (ADS)

Fuchs, Gregory

2011-03-01

Nitrogen vacancy (NV) center spins in diamond have emerged as a promising solid-state system for quantum information processing and precision metrology at room temperature. Understanding and developing the built-in resources of this defect center for quantum logic and memory is critical to achieving these goals. In the first case, we use nanosecond duration microwave manipulation to study the electronic spin of single NV centers in their orbital excited-state (ES). We demonstrate ES Rabi oscillations and use multi-pulse resonant control to differentiate between phonon-induced dephasing, orbital relaxation, and coherent electron-nuclear interactions. A second resource, the nuclear spin of the intrinsic nitrogen atom, may be an ideal candidate for a quantum memory due to both the long coherence of nuclear spins and their deterministic presence. We investigate coherent swaps between the NV center electronic spin state and the nuclear spin state of nitrogen using Landau-Zener transitions performed outside the asymptotic regime. The swap gates are generated using lithographically fabricated waveguides that form a high-bandwidth, two-axis vector magnet on the diamond substrate. These experiments provide tools for coherently manipulating and storing quantum information in a scalable solid-state system at room temperature. We gratefully acknowledge support from AFOSR, ARO, and DARPA.

Spin transport in carbon nanotubes bundles: An ab-initio study

NASA Astrophysics Data System (ADS)

Meena, Shweta; Choudhary, Sudhanshu

2017-10-01

First principles investigations are performed on understanding the spin-polarized transport in carbon nanotubes and carbon nanotube bundles consisting of (8 , 0) and (17 , 0) SWCNTs kept in vertical (out-of-plane) arrangement and contacted by two CrO2 Half-Metallic-Ferromagnetic (HMF) electrodes. On comparison of the results for all the structures, it is observed that carbon nanotube bundle consisting of (17 , 0) CNT offers high TMR ∼100% and the transport phenomenon is tunneling, since there are no transmission states near Fermi level. However, in individual (8 , 0) and (17 , 0) CNT the transport is not because of tunneling, since there are significant number of transmission states near Fermi level. High Magneto Resistance (MR) 96% and 99% is observed in individual (8 , 0) and (17 , 0) CNTs respectively. Both TMR and Spin Injection Efficiency η (Spin-Filtration) are higher in (17 , 0) carbon nanotube bundle structure, which is due to carbon nanotube bundle acting as a perfect barrier in vertical (out-of-plane) arrangement resulting in negligible spin-down current (I↓) in both Parallel Configuration (PC) and Antiparallel Configuration (APC).

Solid state nuclear magnetic resonance with magic-angle spinning and dynamic nuclear polarization below 25 K

PubMed Central

Thurber, Kent R.; Potapov, Alexey; Yau, Wai-Ming; Tycko, Robert

2012-01-01

We describe an apparatus for solid state nuclear magnetic resonance (NMR) with dynamic nuclear polarization (DNP) and magic-angle spinning (MAS) at 20–25 K and 9.4 Tesla. The MAS NMR probe uses helium to cool the sample space and nitrogen gas for MAS drive and bearings, as described earlier (Thurber et al., J. Magn. Reson. 2008) [1], but also includes a corrugated waveguide for transmission of microwaves from below the probe to the sample. With a 30 mW circularly polarized microwave source at 264 GHz, MAS at 6.8 kHz, and 21 K sample temperature, greater than 25-fold enhancements of cross-polarized 13C NMR signals are observed in spectra of frozen glycerol/water solutions containing the triradical dopant DOTOPA-TEMPO when microwaves are applied. As demonstrations, we present DNP-enhanced one-dimensional and two-dimensional 13C MAS NMR spectra of frozen solutions of uniformly 13C-labeled L-alanine and melittin, a 26-residue helical peptide that we have synthesized with four uniformly 13C-labeled amino acids. PMID:23238592

Solid state nuclear magnetic resonance with magic-angle spinning and dynamic nuclear polarization below 25 K.

PubMed

Thurber, Kent R; Potapov, Alexey; Yau, Wai-Ming; Tycko, Robert

2013-01-01

We describe an apparatus for solid state nuclear magnetic resonance (NMR) with dynamic nuclear polarization (DNP) and magic-angle spinning (MAS) at 20-25 K and 9.4 Tesla. The MAS NMR probe uses helium to cool the sample space and nitrogen gas for MAS drive and bearings, as described earlier, but also includes a corrugated waveguide for transmission of microwaves from below the probe to the sample. With a 30 mW circularly polarized microwave source at 264 GHz, MAS at 6.8 kHz, and 21 K sample temperature, greater than 25-fold enhancements of cross-polarized (13)C NMR signals are observed in spectra of frozen glycerol/water solutions containing the triradical dopant DOTOPA-TEMPO when microwaves are applied. As demonstrations, we present DNP-enhanced one-dimensional and two-dimensional (13)C MAS NMR spectra of frozen solutions of uniformly (13)C-labeled l-alanine and melittin, a 26-residue helical peptide that we have synthesized with four uniformly (13)C-labeled amino acids. Published by Elsevier Inc.

Application of ex situ dynamic nuclear polarization in studying small molecules.

PubMed

Ludwig, Christian; Marin-Montesinos, Ildefonso; Saunders, Martin G; Emwas, Abdul-Hamid; Pikramenou, Zoe; Hammond, Stephen P; Günther, Ulrich L

2010-06-14

Dynamic nuclear polarization (DNP) has become an attractive technique to boost the sensitivity of NMR experiments. In the case of ex situ polarizations two-dimensional (2D) spectra are limited by the short lifetime of the polarization after dissolution and sample transfer to a high field NMR magnet. This limitation can be overcome by various approaches. Here we show how the use of (13)C-labelled acetyl tags can help to obtain 2D-HMQC spectra for many small molecules, owing to a nuclear Overhauser enhancement between (13)C spins originating from the long-lived carbonyl carbon, which extends the lifetimes of other (13)C spins with shorter longitudinal relaxation times. We also show an alternative approach of using an optimized polarization matrix.

Spin-lattice relaxation of 13C in solid amino acids using the CP-MAS technique

NASA Astrophysics Data System (ADS)

Naito, A.; Ganapathy, S.; Akasaka, K.; McDowell, C. A.

It is shown by a simple application of relaxation theory that the 13C magnetization decays nonexponentially, in principle, in the CP-MAS experiment because of the distribution of the spin-lattice relaxation times; however, the deviation from the exponential decay is quite small. The transient Overhauser effect also contributes appreciably to the nonexponential decay of the 13C magnetization when the protons are not saturated during the 13C T1 measurements and the correlation time of the group rotational motion satisfies the condition, ω2τc2 ≦ 1. It is shown by both experiment and theory that the transient Overhauser effect in the solid state is much smaller than that expected for the liquid state. The 13C spin-lattice relaxation times of L-alanine, deutero- L-alanine, glycine, and L-serine were determined for the individual carbon atoms. The experimentally obtained 13C T1 values agree well with calculated ones, showing that the CH 3 group rotation provides the main source of the relaxation in alanine, while the NH 3+ group motion plays an important role for the relaxation in glycine and serene.

Quenching of dynamic nuclear polarization by spin-orbit coupling in GaAs quantum dots.

PubMed

Nichol, John M; Harvey, Shannon P; Shulman, Michael D; Pal, Arijeet; Umansky, Vladimir; Rashba, Emmanuel I; Halperin, Bertrand I; Yacoby, Amir

2015-07-17

The central-spin problem is a widely studied model of quantum decoherence. Dynamic nuclear polarization occurs in central-spin systems when electronic angular momentum is transferred to nuclear spins and is exploited in quantum information processing for coherent spin manipulation. However, the mechanisms limiting this process remain only partially understood. Here we show that spin-orbit coupling can quench dynamic nuclear polarization in a GaAs quantum dot, because spin conservation is violated in the electron-nuclear system, despite weak spin-orbit coupling in GaAs. Using Landau-Zener sweeps to measure static and dynamic properties of the electron spin-flip probability, we observe that the size of the spin-orbit and hyperfine interactions depends on the magnitude and direction of applied magnetic field. We find that dynamic nuclear polarization is quenched when the spin-orbit contribution exceeds the hyperfine, in agreement with a theoretical model. Our results shed light on the surprisingly strong effect of spin-orbit coupling in central-spin systems.

On the Usage of Locally Dense Basis Sets in the Calculation of NMR Indirect Nuclear Spin-Spin Coupling Constants

NASA Astrophysics Data System (ADS)

Sanchez, Marina; Provasi, Patricio F.; Aucar, Gustavo A.; Sauer, Stephan P. A.

Locally dense basis sets (nuclear spin-spin couplings in several saturated and unsaturated fluorinated hydrocarbons. We find that the choice of the basis set for each atom belonging to our studied model compounds depends on its location with respect to the coupled fluorine atoms and on the cis/trans or synperiplanar/antiperiplanar conformation of the molecule. Carbon atoms in the bonding path connecting the coupled fluorine atoms have to be described with better basis sets than the carbon atoms outside this path. For the hydrogen atoms directly connected to the coupling pathway in molecules with trans or antiperiplanar conformations and for all hydrogen atoms not directly connected to the coupling pathway one can employ a minimal basis set with only one s-function. Employing these type of LDBSs we can reduce the number of necessary basis functions by about 30% without losing more than about 1 Hz in accuracy. The analysis of the four contributions to the vicinal fluorine-fluorine coupling constants shows that the non-contact orbital paramagnetic term is the most important contribution followed by the also non-contact spin-dipolar term. The Fermi contact term is the largest contribution only in the synperiplanar conformations of 1,2-difluoroethane and -propane.

Thermoelectric unipolar spin battery in a suspended carbon nanotube.

PubMed

Cao, Zhan; Fang, Tie-Feng; He, Wan-Xiu; Luo, Hong-Gang

2017-04-26

A quantum dot formed in a suspended carbon nanotube exposed to an external magnetic field is predicted to act as a thermoelectric unipolar spin battery which generates pure spin current. The built-in spin flip mechanism is a consequence of the spin-vibration interaction resulting from the interplay between the intrinsic spin-orbit coupling and the vibrational modes of the suspended carbon nanotube. On the other hand, utilizing thermoelectric effect, the temperature difference between the electron and the thermal bath to which the vibrational modes are coupled provides the driving force. We find that both magnitude and direction of the generated pure spin current are dependent on the strength of spin-vibration interaction, the sublevel configuration in dot, the temperatures of electron and thermal bath, and the tunneling rate between the dot and the pole. Moreover, in the linear response regime, the kinetic coefficient is non-monotonic in the temperature T and it reaches its maximum when [Formula: see text] is about one phonon energy. The existence of a strong intradot Coulomb interaction is irrelevant for our spin battery, provided that high-order cotunneling processes are suppressed.

CP/MAS /sup 13/C NMR spectroscopic study of chlorophyll a in the solid state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, C.E.; Spencer, R.B.; Burger, V.T.

1983-09-01

Solid-state cross-polarization, magic-angle sample spinning carbon-13 nuclear magnetic resonance spectra have been recorded on chlorophyll a- water aggregates, methyl pyrochlorophyllide a and methyl pyropheophorbide a (derivatives that lack a phytyl chain). Spectra have also been collected under a decoupling regime in which resonances of certain hydrogen-bearing carbon atoms are suppressed. These observations are used to assign the solid state spectra.

Suppression of nuclear spin bath fluctuations in self-assembled quantum dots induced by inhomogeneous strain

PubMed Central

Chekhovich, E.A.; Hopkinson, M.; Skolnick, M.S.; Tartakovskii, A.I.

2015-01-01

Interaction with nuclear spins leads to decoherence and information loss in solid-state electron-spin qubits. One particular, ineradicable source of electron decoherence arises from decoherence of the nuclear spin bath, driven by nuclear–nuclear dipolar interactions. Owing to its many-body nature nuclear decoherence is difficult to predict, especially for an important class of strained nanostructures where nuclear quadrupolar effects have a significant but largely unknown impact. Here, we report direct measurement of nuclear spin bath coherence in individual self-assembled InGaAs/GaAs quantum dots: spin-echo coherence times in the range 1.2–4.5 ms are found. Based on these values, we demonstrate that strain-induced quadrupolar interactions make nuclear spin fluctuations much slower compared with lattice-matched GaAs/AlGaAs structures. Our findings demonstrate that quadrupolar effects can potentially be used to engineer optically active III-V semiconductor spin-qubits with a nearly noise-free nuclear spin bath, previously achievable only in nuclear spin-0 semiconductors, where qubit network interconnection and scaling are challenging. PMID:25704639

Voltage-selective bidirectional polarization and coherent rotation of nuclear spins in quantum dots.

PubMed

Takahashi, R; Kono, K; Tarucha, S; Ono, K

2011-07-08

We propose and demonstrate that the nuclear spins of the host lattice in GaAs double quantum dots can be polarized in either of two opposite directions, parallel or antiparallel to an external magnetic field. The direction is selected by adjusting the dc voltage. This nuclear polarization manifests itself by repeated controlled electron-nuclear spin scattering in the Pauli spin-blockade state. Polarized nuclei are also controlled by means of nuclear magnetic resonance. This Letter confirms that the nuclear spins in quantum dots are long-lived quantum states with a coherence time of up to 1 ms, and may be a promising resource for quantum-information processing such as quantum memories for electron spin qubits.

Nuclear Spin Locking and Extended Two-Electron Spin Decoherence Time in an InAs Quantum Dot Molecule

NASA Astrophysics Data System (ADS)

Chow, Colin; Ross, Aaron; Steel, Duncan; Sham, L. J.; Bracker, Allan; Gammon, Daniel

2015-03-01

The spin eigenstates for two electrons confined in a self-assembled InAs quantum dot molecule (QDM) consist of the spin singlet state, S, with J = 0 and the triplet states T-, T0 and T+, with J = 1. When a transverse magnetic field (Voigt geometry) is applied, the two-electron system can be initialized to the different states with appropriate laser excitation. Under the excitation of a weak probe laser, non-Lorentzian lineshapes are obtained when the system is initialized to either T- or T+, where T- results in a ``resonance locking'' lineshape while T+ gives a ``resonance avoiding '' lineshape: two different manifestations of hysteresis showing the importance of memory in the system. These observations signify dynamic nuclear spin polarization (DNSP) arising from a feedback mechanism involving hyperfine interaction between lattice nuclei and delocalized electron spins, and Overhauser shift due to nuclear spin polarization. Using pump configurations that generate coherent population trapping, the isolation of the electron spin from the optical excitation shows the stabilization of the nuclear spin ensemble. The dark-state lineshape measures the lengthened electron spin decoherence time, from 1 ns to 1 μs. Our detailed spectra highlight the potential of QDM for realizing a two-qubit gate. This work is supported by NSF, ARO, AFOSR, DARPA, and ONR.

Highly selective detection of individual nuclear spins with rotary echo on an electron spin probe

PubMed Central

Mkhitaryan, V. V.; Jelezko, F.; Dobrovitski, V. V.

2015-01-01

We consider an electronic spin, such as a nitrogen-vacancy center in diamond, weakly coupled to a large number of nuclear spins, and subjected to the Rabi driving with a periodically alternating phase. We show that by switching the driving phase synchronously with the precession of a given nuclear spin, the interaction to this spin is selectively enhanced, while the rest of the bath remains decoupled. The enhancement is of resonant character. The key feature of the suggested scheme is that the width of the resonance is adjustable, and can be greatly decreased by increasing the driving strength. Thus, the resonance can be significantly narrowed, by a factor of 10–100 in comparison with the existing detection methods. Significant improvement in selectivity is explained analytically and confirmed by direct numerical many-spin simulations. The method can be applied to a wide range of solid-state systems. PMID:26497777

Optically Induced Nuclear Spin Polarization in the Quantum Hall Regime: The Effect of Electron Spin Polarization through Exciton and Trion Excitations.

PubMed

Akiba, K; Kanasugi, S; Yuge, T; Nagase, K; Hirayama, Y

2015-07-10

We study nuclear spin polarization in the quantum Hall regime through the optically pumped electron spin polarization in the lowest Landau level. The nuclear spin polarization is measured as a nuclear magnetic field B(N) by means of the sensitive resistive detection. We find the dependence of B(N) on the filling factor nonmonotonic. The comprehensive measurements of B(N) with the help of the circularly polarized photoluminescence measurements indicate the participation of the photoexcited complexes, i.e., the exciton and trion (charged exciton), in nuclear spin polarization. On the basis of a novel estimation method of the equilibrium electron spin polarization, we analyze the experimental data and conclude that the filling factor dependence of B(N) is understood by the effect of electron spin polarization through excitons and trions.

Quantitative solid-state 13C nuclear magnetic resonance spectrometric analyses of wood xylen: effect of increasing carbohydrate content

USGS Publications Warehouse

Bates, A.L.; Hatcher, P.G.

1992-01-01

Isolated lignin with a low carbohydrate content was spiked with increasing amounts of alpha-cellulose, and then analysed by solid-state 13C nuclear magnetic resonance (NMR) using cross-polarization with magic angle spinning (CPMAS) and dipolar dephasing methods in order to assess the quantitative reliability of CPMAS measurement of carbohydrate content and to determine how increasingly intense resonances for carbohydrate carbons affect calculations of the degree of lignin's aromatic ring substitution and methoxyl carbon content. Comparisons were made of the carbohydrate content calculated by NMR with carbohydrate concentrations obtained by phenol-sulfuric acid assay and by the calculation from the known amounts of cellulose added. The NMR methods used in this study yield overestimates for carbohydrate carbons due to resonance area overlap from the aliphatic side chain carbons of lignin. When corrections are made for these overlapping resonance areas, the NMR results agree very well with results obtained by other methods. Neither the calculated methoxyl carbon content nor the degree of aromatic ring substitution in lignin, both calculated from dipolar dephasing spectra, change with cellulose content. Likewise, lignin methoxyl content does not correlate with cellulose abundance when measured by integration of CPMAS spectra. ?? 1992.

General theory of feedback control of a nuclear spin ensemble in quantum dots

NASA Astrophysics Data System (ADS)

Yang, Wen; Sham, L. J.

2013-12-01

We present a microscopic theory of the nonequilibrium nuclear spin dynamics driven by the electron and/or hole under continuous-wave pumping in a quantum dot. We show the correlated dynamics of the nuclear spin ensemble and the electron and/or hole under optical excitation as a quantum feedback loop and investigate the dynamics of the many nuclear spins as a nonlinear collective motion. This gives rise to three observable effects: (i) hysteresis, (ii) locking (avoidance) of the pump absorption strength to (from) the natural resonance, and (iii) suppression (amplification) of the fluctuation of weakly polarized nuclear spins, leading to prolonged (shortened) electron-spin coherence time. A single nonlinear feedback function is constructed which determines the different outcomes of the three effects listed above depending on the feedback being negative or positive. The general theory also helps to put in perspective the wide range of existing theories on the problem of a single electron spin in a nuclear spin bath.

Electron Spin Resonance Studies of Carbonic Anhydrase: Transition Metal Ions and Spin-Labeled Sulfonamides*

PubMed Central

Taylor, June S.; Mushak, Paul; Coleman, Joseph E.

1970-01-01

Electron spin resonance (esr) spectra of Cu(II) and Co(II) carbonic anhydrase, and a spin-labeled sulfonamide complex of the Zn(II) enzyme, are reported. The coordination geometry of Cu(II) bound in the enzyme appears to have approximately axial symmetry. Esr spectra of enzyme complexes with metal-binding anions also show axial symmetry and greater covalency, in the order ethoxzolamide < SH- < N3- ≤ CN-. Well-resolved superhyperfine structure in the spectrum of the cyanide complex suggests the presence of two, and probably three, equivalent nitrogen ligands from the protein. Esr spectra of the Co(II) enzyme and its complexes show two types of Co(II) environment, one typical of the native enzyme and the 1:1 CN- complex, and one typical of a 2:1 CN- complex. Co(II) in the 2:1 complex appears to be low-spin and probably has a coordination number of 5. Binding of a spin-labeled sulfonamide to the active center immobilizes the free radical. The similarity of the esr spectra of spin-labeled Zn(II) and Co(II) carbonic anhydrases suggests that the conformation at the active center is similar in the two metal derivatives. PMID:4320976

Theory of long-lived nuclear spin states in methyl groups and quantum-rotor induced polarisation.

PubMed

Dumez, Jean-Nicolas; Håkansson, Pär; Mamone, Salvatore; Meier, Benno; Stevanato, Gabriele; Hill-Cousins, Joseph T; Roy, Soumya Singha; Brown, Richard C D; Pileio, Giuseppe; Levitt, Malcolm H

2015-01-28

Long-lived nuclear spin states have a relaxation time much longer than the longitudinal relaxation time T1. Long-lived states extend significantly the time scales that may be probed with magnetic resonance, with possible applications to transport and binding studies, and to hyperpolarised imaging. Rapidly rotating methyl groups in solution may support a long-lived state, consisting of a population imbalance between states of different spin exchange symmetries. Here, we expand the formalism for describing the behaviour of long-lived nuclear spin states in methyl groups, with special attention to the hyperpolarisation effects observed in (13)CH3 groups upon rapidly converting a material with low-barrier methyl rotation from the cryogenic solid state to a room-temperature solution [M. Icker and S. Berger, J. Magn. Reson. 219, 1 (2012)]. We analyse the relaxation properties of methyl long-lived states using semi-classical relaxation theory. Numerical simulations are supplemented with a spherical-tensor analysis, which captures the essential properties of methyl long-lived states.

Highly selective detection of individual nuclear spins with rotary echo on an electron spin probe

DOE PAGES

Mkhitaryan, V. V.; Jelezko, F.; Dobrovitski, V. V.

2015-10-26

We consider an electronic spin, such as a nitrogen-vacancy center in diamond, weakly coupled to a large number of nuclear spins, and subjected to the Rabi driving with a periodically alternating phase. We show that by switching the driving phase synchronously with the precession of a given nuclear spin, the interaction to this spin is selectively enhanced, while the rest of the bath remains decoupled. The enhancement is of resonant character. The key feature of the suggested scheme is that the width of the resonance is adjustable, and can be greatly decreased by increasing the driving strength. Thus, the resonancemore » can be significantly narrowed, by a factor of 10–100 in comparison with the existing detection methods. Significant improvement in selectivity is explained analytically and confirmed by direct numerical many-spin simulations. As a result, the method can be applied to a wide range of solid-state systems.« less

Optical pumping of electron and nuclear spin in a negatively-charged quantum dot

NASA Astrophysics Data System (ADS)

Bracker, Allan; Gershoni, David; Korenev, Vladimir

2005-03-01

We report optical pumping of electron and nuclear spins in an individual negatively-charged quantum dot. With a bias-controlled heterostructure, we inject one electron into the quantum dot. Intense laser excitation produces negative photoluminescence polarization, which is easily erased by the Hanle effect, demonstrating optical pumping of a long-lived resident electron. The electron spin lifetime is consistent with the influence of nuclear spin fluctuations. Measuring the Overhauser effect in high magnetic fields, we observe a high degree of nuclear spin polarization, which is closely correlated to electron spin pumping.

Electron spin relaxation in carbon nanotubes: Dyakonov-Perel mechanism

NASA Astrophysics Data System (ADS)

Semenov, Yuriy; Zavada, John; Kim, Ki Wook

2010-03-01

The long standing problem of unaccountable short spin relaxation in carbon nanotubes (CNT) meets a disclosure in terms of curvature-mediated spin-orbital interaction that leads to spin fluctuating precession analogous to Dyakonov-Perel mechanism. Strong anisotropy imposed by arbitrary directed magnetic field has been taken into account in terms of extended Bloch equations. Especially, stationary spin current through CNT can be controlled by spin-flip processes with relaxation time as less as 150 ps, the rate of transversal polarization (i.e. decoherence) runs up to 1/(70 ps) at room temperature while spin interference of the electrons related to different valleys can be responsible for shorter spin dephasing. Dependencies of spin-relaxation parameters on magnetic field strength and orientation, CNT curvature and chirality have been analyzed.

Fictitious spin-12 operators and correlations in quadrupole nuclear spin system

NASA Astrophysics Data System (ADS)

Furman, G. B.; Goren, S. D.; Meerovich, V. M.; Sokolovsky, V. L.

The Hamiltonian and the spin operators for a spin 3/2 are represented in the basis formed by the Kronecker productions of the 2×2 Pauli matrices. This reformulation allows us to represent a spin 3/2 as a system of two coupled fictitious spins 1/2. Correlations between these fictitious spins are studied using well-developed methods. We investigate the temperature and field dependences of correlations, such as mutual information, classical correlations, entanglement, and geometric and quantum discords in the fictitious spin-1/2 system describing a nuclear spin 3/2 which is placed in magnetic and inhomogeneous electric fields. It is shown that the correlations between the fictitious spins demonstrate properties which differ from those of real two-spin systems. In contrast to real systems all the correlations between the fictitious spins do not vanish with increasing external magnetic field; at a high magnetic field the correlations tend to their limiting values. Classical correlations, quantum and geometric discords reveal a pronounced asymmetry relative to the measurements on subsystems (fictitious spins) even in a uniform magnetic field and at symmetrical EFG, η=0. The correlations depend also on the distribution of external charges, on the parameter of symmetry η. At η≠0 quantum and geometric discords have finite values in a zero magnetic field. The proposed approach may be useful in analysis of properties of particles with larger angular momentum, can provide the way to discover new physical phenomenon of quantum correlations, and can be a useful tool for similar definitions of other physical quantities of complex systems.

Theoretical aspects of Magic Angle Spinning - Dynamic Nuclear Polarization

NASA Astrophysics Data System (ADS)

Mentink-Vigier, Frederic; Akbey, Ümit; Oschkinat, Hartmut; Vega, Shimon; Feintuch, Akiva

2015-09-01

Magic Angle Spinning (MAS) combined with Dynamic Nuclear Polarization (DNP) has been proven in recent years to be a very powerful method for increasing solid-state NMR signals. Since the advent of biradicals such as TOTAPOL to increase the nuclear polarization new classes of radicals, with larger molecular weight and/or different spin properties have been developed. These have led to unprecedented signal gain, with varying results for different experimental parameters, in particular the microwave irradiation strength, the static field, and the spinning frequency. Recently it has been demonstrated that sample spinning imposes DNP enhancement processes that differ from the active DNP mechanism in static samples as upon sample spinning the DNP enhancements are the results of energy level anticrossings occurring periodically during each rotor cycle. In this work we present experimental results with regards to the MAS frequency dependence of the DNP enhancement profiles of four nitroxide-based radicals at two different sets of temperature, 110 and 160 K. In fact, different magnitudes of reduction in enhancement are observed with increasing spinning frequency. Our simulation code for calculating MAS-DNP powder enhancements of small model spin systems has been improved to extend our studies of the influence of the interaction and relaxation parameters on powder enhancements. To achieve a better understanding we simulated the spin dynamics of a single three-spin system {ea -eb - n } during its steady state rotor periods and used the Landau-Zener formula to characterize the influence of the different anti-crossings on the polarizations of the system and their necessary action for reaching steady state conditions together with spin relaxation processes. Based on these model calculations we demonstrate that the maximum steady state nuclear polarization cannot become larger than the maximum polarization difference between the two electrons during the steady state rotor cycle

Schemes of detecting nuclear spin correlations by dynamical decoupling based quantum sensing

NASA Astrophysics Data System (ADS)

Ma, Wen-Long Ma; Liu, Ren-Bao

Single-molecule sensitivity of nuclear magnetic resonance (NMR) and angstrom resolution of magnetic resonance imaging (MRI) are the highest challenges in magnetic microscopy. Recent development in dynamical decoupling (DD) enhanced diamond quantum sensing has enabled NMR of single nuclear spins and nanoscale NMR. Similar to conventional NMR and MRI, current DD-based quantum sensing utilizes the frequency fingerprints of target nuclear spins. Such schemes, however, cannot resolve different nuclear spins that have the same noise frequency or differentiate different types of correlations in nuclear spin clusters. Here we show that the first limitation can be overcome by using wavefunction fingerprints of target nuclear spins, which is much more sensitive than the ''frequency fingerprints'' to weak hyperfine interaction between the targets and a sensor, while the second one can be overcome by a new design of two-dimensional DD sequences composed of two sets of periodic DD sequences with different periods, which can be independently set to match two different transition frequencies. Our schemes not only offer an approach to breaking the resolution limit set by ''frequency gradients'' in conventional MRI, but also provide a standard approach to correlation spectroscopy for single-molecule NMR.

Symmetry rules for the indirect nuclear spin-spin coupling tensor revisited

NASA Astrophysics Data System (ADS)

Buckingham, A. D.; Pyykkö, P.; Robert, J. B.; Wiesenfeld, L.

The symmetry rules of Buckingham and Love (1970), relating the number of independent components of the indirect spin-spin coupling tensor J to the symmetry of the nuclear sites, are shown to require modification if the two nuclei are exchanged by a symmetry operation. In that case, the anti-symmetric part of J does not transform as a second-rank polar tensor under symmetry operations that interchange the coupled nuclei and may be called an anti-tensor. New rules are derived and illustrated by simple molecular models.

Quantum decoherence dynamics of divacancy spins in silicon carbide.

PubMed

Seo, Hosung; Falk, Abram L; Klimov, Paul V; Miao, Kevin C; Galli, Giulia; Awschalom, David D

2016-09-29

Long coherence times are key to the performance of quantum bits (qubits). Here, we experimentally and theoretically show that the Hahn-echo coherence time of electron spins associated with divacancy defects in 4H-SiC reaches 1.3 ms, one of the longest Hahn-echo coherence times of an electron spin in a naturally isotopic crystal. Using a first-principles microscopic quantum-bath model, we find that two factors determine the unusually robust coherence. First, in the presence of moderate magnetic fields (30 mT and above), the 29 Si and 13 C paramagnetic nuclear spin baths are decoupled. In addition, because SiC is a binary crystal, homo-nuclear spin pairs are both diluted and forbidden from forming strongly coupled, nearest-neighbour spin pairs. Longer neighbour distances result in fewer nuclear spin flip-flops, a less fluctuating intra-crystalline magnetic environment, and thus a longer coherence time. Our results point to polyatomic crystals as promising hosts for coherent qubits in the solid state.

Quantum Information Processing with Large Nuclear Spins in GaAs Semiconductors

NASA Astrophysics Data System (ADS)

Leuenberger, Michael N.; Loss, Daniel; Poggio, M.; Awschalom, D. D.

2002-10-01

We propose an implementation for quantum information processing based on coherent manipulations of nuclear spins I=3/2 in GaAs semiconductors. We describe theoretically an NMR method which involves multiphoton transitions and which exploits the nonequidistance of nuclear spin levels due to quadrupolar splittings. Starting from known spin anisotropies we derive effective Hamiltonians in a generalized rotating frame, valid for arbitrary I, which allow us to describe the nonperturbative time evolution of spin states generated by magnetic rf fields. We identify an experimentally observable regime for multiphoton Rabi oscillations. In the nonlinear regime, we find Berry phase interference.

Nuclear spin relaxation of methane in solid xenon

NASA Astrophysics Data System (ADS)

Sugimoto, Takeru; Arakawa, Ichiro; Yamakawa, Koichiro

2018-03-01

Nuclear spin relaxation of methane in solid xenon has been studied by infrared spectroscopy. From the analysis of the temporal changes of the rovibrational peaks, the rates of the nuclear spin relaxation of I = 2 ← 1 correlated to the rotational relaxation of J = 0 ← 1 were obtained at temperatures of 5.1-11.5 K. On the basis of the temperature dependence of the relaxation rate, the activation energy of the indirect two-phonon process was determined to be 50 ± 6 K, which is in good agreement with the rotational transition energies of J = 2 ← 1 and J = 3 ← 1. Taking into account this result and the spin degeneracy, we argue that the lowest J = 3 level in which the I = 1 and I = 2 states are degenerate acts as the intermediate point of the indirect process.

Noise-Resilient Quantum Computing with a Nitrogen-Vacancy Center and Nuclear Spins.

PubMed

Casanova, J; Wang, Z-Y; Plenio, M B

2016-09-23

Selective control of qubits in a quantum register for the purposes of quantum information processing represents a critical challenge for dense spin ensembles in solid-state systems. Here we present a protocol that achieves a complete set of selective electron-nuclear gates and single nuclear rotations in such an ensemble in diamond facilitated by a nearby nitrogen-vacancy (NV) center. The protocol suppresses internuclear interactions as well as unwanted coupling between the NV center and other spins of the ensemble to achieve quantum gate fidelities well exceeding 99%. Notably, our method can be applied to weakly coupled, distant spins representing a scalable procedure that exploits the exceptional properties of nuclear spins in diamond as robust quantum memories.

Theoretical aspects of Magic Angle Spinning - Dynamic Nuclear Polarization.

PubMed

Mentink-Vigier, Frederic; Akbey, Ümit; Oschkinat, Hartmut; Vega, Shimon; Feintuch, Akiva

2015-09-01

Magic Angle Spinning (MAS) combined with Dynamic Nuclear Polarization (DNP) has been proven in recent years to be a very powerful method for increasing solid-state NMR signals. Since the advent of biradicals such as TOTAPOL to increase the nuclear polarization new classes of radicals, with larger molecular weight and/or different spin properties have been developed. These have led to unprecedented signal gain, with varying results for different experimental parameters, in particular the microwave irradiation strength, the static field, and the spinning frequency. Recently it has been demonstrated that sample spinning imposes DNP enhancement processes that differ from the active DNP mechanism in static samples as upon sample spinning the DNP enhancements are the results of energy level anticrossings occurring periodically during each rotor cycle. In this work we present experimental results with regards to the MAS frequency dependence of the DNP enhancement profiles of four nitroxide-based radicals at two different sets of temperature, 110 and 160K. In fact, different magnitudes of reduction in enhancement are observed with increasing spinning frequency. Our simulation code for calculating MAS-DNP powder enhancements of small model spin systems has been improved to extend our studies of the influence of the interaction and relaxation parameters on powder enhancements. To achieve a better understanding we simulated the spin dynamics of a single three-spin system {ea-eb-n} during its steady state rotor periods and used the Landau-Zener formula to characterize the influence of the different anti-crossings on the polarizations of the system and their necessary action for reaching steady state conditions together with spin relaxation processes. Based on these model calculations we demonstrate that the maximum steady state nuclear polarization cannot become larger than the maximum polarization difference between the two electrons during the steady state rotor cycle. This

Measuring absolute spin polarization in dissolution-DNP by Spin PolarimetrY Magnetic Resonance (SPY-MR)

NASA Astrophysics Data System (ADS)

Vuichoud, Basile; Milani, Jonas; Chappuis, Quentin; Bornet, Aurélien; Bodenhausen, Geoffrey; Jannin, Sami

2015-11-01

Dynamic nuclear polarization at 1.2 K and 6.7 T allows one to achieve spin temperatures on the order of a few millikelvin, so that the high-temperature approximation (Δ E < kT) is violated for the nuclear Zeeman interaction Δ E = γB0h/(2 π) of most isotopes. Provided that, after rapid dissolution and transfer to an NMR or MRI system, the hyperpolarized molecules contain at least two nuclear spins I and S with a scalar coupling JIS, the polarization of spin I (short for 'investigated') can be determined from the asymmetry AS of the multiplet of spin S (short for 'spy'), provided perturbations due to second-order (strong coupling) effects are properly taken into account. If spin S is suitably discreet and does not affect the relaxation of spin I, this provides an elegant way of measuring spin polarizations 'on the fly' in a broad range of molecules, thus obviating the need for laborious measurements of signal intensities at thermal equilibrium. The method, dubbed Spin PolarimetrY Magnetic Resonance (SPY-MR), is illustrated for various pairs of 13 C spins (I, S) in acetate and pyruvate.

Quantum Information Processing with Large Nuclear Spins in GaAs Semiconductors

NASA Astrophysics Data System (ADS)

Leuenberger, Michael N.; Loss, Daniel; Poggio, M.; Awschalom, D. D.

2003-03-01

We propose an implementation for quantum information processing based on coherent manipulations of nuclear spins I=3/2 in GaAs semiconductors. We describe theoretically an NMR method which involves multiphoton transitions and which exploits the nonequidistance of nuclear spin levels due to quadrupolar splittings. Starting from known spin anisotropies we derive effective Hamiltonians in a generalized rotating frame, valid for arbitrary I, which allow us to describe the nonperturbative time evolution of spin states generated by magnetic rf fields. We identify an experimentally observable regime for multiphoton Rabi oscillations. In the nonlinear regime, we find Berry phase interference. Ref: PRL 89, 207601 (2002).

Room-temperature coupling between electrical current and nuclear spins in OLEDs

NASA Astrophysics Data System (ADS)

Malissa, H.; Kavand, M.; Waters, D. P.; van Schooten, K. J.; Burn, P. L.; Vardeny, Z. V.; Saam, B.; Lupton, J. M.; Boehme, C.

2014-09-01

The effects of external magnetic fields on the electrical conductivity of organic semiconductors have been attributed to hyperfine coupling of the spins of the charge carriers and hydrogen nuclei. We studied this coupling directly by implementation of pulsed electrically detected nuclear magnetic resonance spectroscopy in organic light-emitting diodes (OLEDs). The data revealed a fingerprint of the isotope (protium or deuterium) involved in the coherent spin precession observed in spin-echo envelope modulation. Furthermore, resonant control of the electric current by nuclear spin orientation was achieved with radiofrequency pulses in a double-resonance scheme, implying current control on energy scales one-millionth the magnitude of the thermal energy.

C-13 nuclear magnetic resonance in graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Resing, H. A.

1985-01-01

The C-13 NMR chemical shifts of graphite intercalation compounds have been calculated. For acceptor types, the shifts come mainly from the paramagnetic (Ramsey) intra-atomic terms. They are related to the gross features of the two-dimensional band structures. The calculated anisotropy is about - 140 ppm and is independent of the finer details such as charge transfer. For donor types, the carbon 2p pi orbitals are spin-polarized because of mixing with metal-conduction electrons, thus there is an additional dipolar contribution which may be correlated with the electronic specific heat. The general agreement with experimental data is satisfactory.

Spin Noise Detection of Nuclear Hyperpolarization at 1.2 K

PubMed Central

Pöschko, Maria Theresia; Vuichoud, Basile; Milani, Jonas; Bornet, Aurélien; Bechmann, Matthias; Bodenhausen, Geoffrey; Jannin, Sami; Müller, Norbert

2015-01-01

We report proton spin noise spectra of a hyperpolarized solid sample of commonly used “DNP (dynamic nuclear polarization) juice” containing TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidine N-oxide) and irradiated by a microwave field at a temperature of 1.2 K in a magnetic field of 6.7 T. The line shapes of the spin noise power spectra are sensitive to the variation of the microwave irradiation frequency and change from dip to bump, when the electron Larmor frequency is crossed, which is shown to be in good accordance with theory by simulations. Small but significant deviations from these predictions are observed, which can be related to spin noise and radiation damping phenomena that have been reported in thermally polarized systems. The non-linear dependence of the spin noise integral on nuclear polarization provides a means to monitor hyperpolarization semi-quantitatively without any perturbation of the spin system by radio frequency irradiation. PMID:26477605

Low-temperature dynamic nuclear polarization with helium-cooled samples and nitrogen-driven magic-angle spinning.

PubMed

Thurber, Kent; Tycko, Robert

2016-03-01

We describe novel instrumentation for low-temperature solid state nuclear magnetic resonance (NMR) with dynamic nuclear polarization (DNP) and magic-angle spinning (MAS), focusing on aspects of this instrumentation that have not been described in detail in previous publications. We characterize the performance of an extended interaction oscillator (EIO) microwave source, operating near 264 GHz with 1.5 W output power, which we use in conjunction with a quasi-optical microwave polarizing system and a MAS NMR probe that employs liquid helium for sample cooling and nitrogen gas for sample spinning. Enhancement factors for cross-polarized (13)C NMR signals in the 100-200 range are demonstrated with DNP at 25K. The dependences of signal amplitudes on sample temperature, as well as microwave power, polarization, and frequency, are presented. We show that sample temperatures below 30K can be achieved with helium consumption rates below 1.3 l/h. To illustrate potential applications of this instrumentation in structural studies of biochemical systems, we compare results from low-temperature DNP experiments on a calmodulin-binding peptide in its free and bound states. Published by Elsevier Inc.

Manipulation of a Nuclear Spin by a Magnetic Domain Wall in a Quantum Hall Ferromagnet.

PubMed

Korkusinski, M; Hawrylak, P; Liu, H W; Hirayama, Y

2017-03-06

The manipulation of a nuclear spin by an electron spin requires the energy to flip the electron spin to be vanishingly small. This can be realized in a many electron system with degenerate ground states of opposite spin polarization in different Landau levels. We present here a microscopic theory of a domain wall between spin unpolarized and spin polarized quantum Hall ferromagnet states at filling factor two with the Zeeman energy comparable to the cyclotron energy. We determine the energies and many-body wave functions of the electronic quantum Hall droplet with up to N = 80 electrons as a function of the total spin, angular momentum, cyclotron and Zeeman energies from the spin singlet ν = 2 phase, through an intermediate polarization state exhibiting a domain wall to the fully spin-polarized phase involving the lowest and the second Landau levels. We demonstrate that the energy needed to flip one electron spin in a domain wall becomes comparable to the energy needed to flip the nuclear spin. The orthogonality of orbital electronic states is overcome by the many-electron character of the domain - the movement of the domain wall relative to the position of the nuclear spin enables the manipulation of the nuclear spin by electrical means.

Manipulation of a Nuclear Spin by a Magnetic Domain Wall in a Quantum Hall Ferromagnet

PubMed Central

Korkusinski, M.; Hawrylak, P.; Liu, H. W.; Hirayama, Y.

2017-01-01

The manipulation of a nuclear spin by an electron spin requires the energy to flip the electron spin to be vanishingly small. This can be realized in a many electron system with degenerate ground states of opposite spin polarization in different Landau levels. We present here a microscopic theory of a domain wall between spin unpolarized and spin polarized quantum Hall ferromagnet states at filling factor two with the Zeeman energy comparable to the cyclotron energy. We determine the energies and many-body wave functions of the electronic quantum Hall droplet with up to N = 80 electrons as a function of the total spin, angular momentum, cyclotron and Zeeman energies from the spin singlet ν = 2 phase, through an intermediate polarization state exhibiting a domain wall to the fully spin-polarized phase involving the lowest and the second Landau levels. We demonstrate that the energy needed to flip one electron spin in a domain wall becomes comparable to the energy needed to flip the nuclear spin. The orthogonality of orbital electronic states is overcome by the many-electron character of the domain - the movement of the domain wall relative to the position of the nuclear spin enables the manipulation of the nuclear spin by electrical means. PMID:28262758

Quantum decoherence dynamics of divacancy spins in silicon carbide

DOE PAGES

Seo, Hosung; Falk, Abram L.; Klimov, Paul V.; ...

2016-09-29

Long coherence times are key to the performance of quantum bits (qubits). Here, we experimentally and theoretically show that the Hahn-echo coherence time of electron spins associated with divacancy defects in 4H-SiC reaches 1.3 ms, one of the longest Hahn-echo coherence times of an electron spin in a naturally isotopic crystal. Using a first-principles microscopic quantum-bath model, we find that two factors determine the unusually robust coherence. First, in the presence of moderate magnetic fields (30mT and above), the 29Si and 13C paramagnetic nuclear spin baths are decoupled. In addition, because SiC is a binary crystal, homo-nuclear spin pairs aremore » both diluted and forbidden from forming strongly coupled, nearest-neighbour spin pairs. Longer neighbour distances result in fewer nuclear spin flip-flops, a less fluctuating intra-crystalline magnetic environment, and thus a longer coherence time. Lastly, our results point to polyatomic crystals as promising hosts for coherent qubits in the solid state.« less

Dynamic nuclear spin polarization in the resonant laser excitation of an InGaAs quantum dot.

PubMed

Högele, A; Kroner, M; Latta, C; Claassen, M; Carusotto, I; Bulutay, C; Imamoglu, A

2012-05-11

Resonant optical excitation of lowest-energy excitonic transitions in self-assembled quantum dots leads to nuclear spin polarization that is qualitatively different from the well-known optical orientation phenomena. By carrying out a comprehensive set of experiments, we demonstrate that nuclear spin polarization manifests itself in quantum dots subjected to finite external magnetic field as locking of the higher energy Zeeman transition to the driving laser field, as well as the avoidance of the resonance condition for the lower energy Zeeman branch. We interpret our findings on the basis of dynamic nuclear spin polarization originating from noncollinear hyperfine interaction and find excellent agreement between experiment and theory. Our results provide evidence for the significance of noncollinear hyperfine processes not only for nuclear spin diffusion and decay, but also for buildup dynamics of nuclear spin polarization in a coupled electron-nuclear spin system.

Selective Optical Addressing of Nuclear Spins through Superhyperfine Interaction in Rare-Earth Doped Solids.

PubMed

Car, B; Veissier, L; Louchet-Chauvet, A; Le Gouët, J-L; Chanelière, T

2018-05-11

In Er^{3+}:Y_{2}SiO_{5}, we demonstrate the selective optical addressing of the ^{89}Y^{3+} nuclear spins through their superhyperfine coupling with the Er^{3+} electronic spins possessing large Landé g factors. We experimentally probe the electron-nuclear spin mixing with photon echo techniques and validate our model. The site-selective optical addressing of the Y^{3+} nuclear spins is designed by adjusting the magnetic field strength and orientation. This constitutes an important step towards the realization of long-lived solid-state qubits optically addressed by telecom photons.

Orphan spin operators enable the acquisition of multiple 2D and 3D magic angle spinning solid-state NMR spectra

NASA Astrophysics Data System (ADS)

Gopinath, T.; Veglia, Gianluigi

2013-05-01

We propose a general method that enables the acquisition of multiple 2D and 3D solid-state NMR spectra for U-13C, 15N-labeled proteins. This method, called MEIOSIS (Multiple ExperIments via Orphan SpIn operatorS), makes it possible to detect four coherence transfer pathways simultaneously, utilizing orphan (i.e., neglected) spin operators of nuclear spin polarization generated during 15N-13C cross polarization (CP). In the MEIOSIS experiments, two phase-encoded free-induction decays are decoded into independent nuclear polarization pathways using Hadamard transformations. As a proof of principle, we show the acquisition of multiple 2D and 3D spectra of U-13C, 15N-labeled microcrystalline ubiquitin. Hadamard decoding of CP coherences into multiple independent spin operators is a new concept in solid-state NMR and is extendable to many other multidimensional experiments. The MEIOSIS method will increase the throughput of solid-state NMR techniques for microcrystalline proteins, membrane proteins, and protein fibrils.

High polarization of nuclear spins mediated by nanoparticles at millikelvin temperatures.

PubMed

Owers-Bradley, John R; Horsewill, Anthony J; Peat, David T; Goh, Kelvin S K; Gadian, David G

2013-07-07

Nuclear magnetic resonance (NMR) techniques are extensively used in many areas of basic and clinical research, as well as in diagnostic medicine. However, NMR signals are intrinsically weak, and this imposes substantial constraints on the amounts and concentrations of materials that can be detected. The signals are weak because of the low energies characteristic of NMR and the resulting very low (typically 0.0001-0.01%) polarization of the nuclear spins. Here, we show that exposure to very low temperatures and high magnetic fields, in conjunction with nanoparticle-mediated relaxation enhancement, can be used to generate extremely high nuclear polarization levels on a realistic timescale; with copper nanoparticles at 15 mK and 14 T, (13)C polarization grew towards its equilibrium level of 23% with an estimated half-time of about 60 hours. This contrasts with a (13)C half-time of at least one year in the presence of aluminium nanoparticles. Cupric oxide nanoparticles were also effective relaxation agents. Our findings lead us to suspect that the relaxation may be mediated, at least in part, by the remarkable magnetic properties that some nanoparticle preparations can display. This methodology offers prospects for achieving polarization levels of 10-50% or more for many nuclear species, with a wide range of potential applications in structural biology and medicine.

Investigation of the Possibility of Using Nuclear Magnetic Spin Alignment

NASA Technical Reports Server (NTRS)

Dent, William V., Jr.

1998-01-01

The goal of the program to investigate a "Gasdynamic fusion propulsion system for space exploration" is to develop a fusion propulsion system for a manned mission to the planet mars. A study using Deuterium and Tritium atoms are currently in progress. When these atoms under-go fusion, the resulting neutrons and alpha particles are emitted in random directions (isotropically). The probable direction of emission is equal for all directions, thus resulting in wasted energy, massive shielding and cooling requirements, and serious problems with the physics of achieving fusion. If the nuclear magnetic spin moments of the deuterium and tritium nuclei could be precisely aligned at the moment of fusion, the stream of emitted neutrons could be directed out the rear of the spacecraft for thrust and the alpha particles directed forward into an electromagnet ot produce electricity to continue operating the fusion engine. The following supporting topics are discussed: nuclear magnetic moments and spin precession in magnetic field, nuclear spin quantum mechanics, kinematics of nuclear reactions, and angular distribution of particles.

Distinction of nuclear spin states with the scanning tunneling microscope.

PubMed

Natterer, Fabian Donat; Patthey, François; Brune, Harald

2013-10-25

We demonstrate rotational excitation spectroscopy with the scanning tunneling microscope for physisorbed H(2) and its isotopes HD and D(2). The observed excitation energies are very close to the gas phase values and show the expected scaling with the moment of inertia. Since these energies are characteristic for the molecular nuclear spin states we are able to identify the para and ortho species of hydrogen and deuterium, respectively. We thereby demonstrate nuclear spin sensitivity with unprecedented spatial resolution.

Multinuclear Detection of Nuclear Spin Optical Rotation at Low Field.

PubMed

Zhu, Yue; Gao, Yuheng; Rodocker, Shane; Savukov, Igor; Hilty, Christian

2018-06-06

We describe the multinuclear detection of nuclear spin optical rotation (NSOR), an effect dependent on the hyperfine interaction between nuclear spins and electrons. Signals of 1 H and 19 F are discriminated by frequency in a single spectrum acquired at sub-millitesla field. The simultaneously acquired optical signal along with the nuclear magnetic resonance signal allows the calculation of the relative magnitude of the NSOR constants corresponding to different nuclei within the sample molecules. This is illustrated by a larger NSOR signal measured at the 19 F frequency despite a smaller corresponding spin concentration. Second, it is shown that heteronuclear J-coupling is observable in the NSOR signal, which can be used to retrieve chemical information. Multinuclear frequency and J resolution can localize optical signals in the molecule. Properties of electronic states at multiple sites in a molecule may therefore ultimately be determined by frequency-resolved NSOR spectroscopy at low field.

Delayed entanglement echo for individual control of a large number of nuclear spins

PubMed Central

Wang, Zhen-Yu; Casanova, Jorge; Plenio, Martin B.

2017-01-01

Methods to selectively detect and manipulate nuclear spins by single electrons of solid-state defects play a central role for quantum information processing and nanoscale nuclear magnetic resonance (NMR). However, with standard techniques, no more than eight nuclear spins have been resolved by a single defect centre. Here we develop a method that improves significantly the ability to detect, address and manipulate nuclear spins unambiguously and individually in a broad frequency band by using a nitrogen-vacancy (NV) centre as model system. On the basis of delayed entanglement control, a technique combining microwave and radio frequency fields, our method allows to selectively perform robust high-fidelity entangling gates between hardly resolved nuclear spins and the NV electron. Long-lived qubit memories can be naturally incorporated to our method for improved performance. The application of our ideas will increase the number of useful register qubits accessible to a defect centre and improve the signal of nanoscale NMR. PMID:28256508

Delayed entanglement echo for individual control of a large number of nuclear spins.

PubMed

Wang, Zhen-Yu; Casanova, Jorge; Plenio, Martin B

2017-03-03

Methods to selectively detect and manipulate nuclear spins by single electrons of solid-state defects play a central role for quantum information processing and nanoscale nuclear magnetic resonance (NMR). However, with standard techniques, no more than eight nuclear spins have been resolved by a single defect centre. Here we develop a method that improves significantly the ability to detect, address and manipulate nuclear spins unambiguously and individually in a broad frequency band by using a nitrogen-vacancy (NV) centre as model system. On the basis of delayed entanglement control, a technique combining microwave and radio frequency fields, our method allows to selectively perform robust high-fidelity entangling gates between hardly resolved nuclear spins and the NV electron. Long-lived qubit memories can be naturally incorporated to our method for improved performance. The application of our ideas will increase the number of useful register qubits accessible to a defect centre and improve the signal of nanoscale NMR.

Measuring absolute spin polarization in dissolution-DNP by Spin PolarimetrY Magnetic Resonance (SPY-MR).

PubMed

Vuichoud, Basile; Milani, Jonas; Chappuis, Quentin; Bornet, Aurélien; Bodenhausen, Geoffrey; Jannin, Sami

2015-11-01

Dynamic nuclear polarization at 1.2 K and 6.7 T allows one to achieve spin temperatures on the order of a few millikelvin, so that the high-temperature approximation (ΔEnuclear Zeeman interaction ΔE=γB0h/(2π) of most isotopes. Provided that, after rapid dissolution and transfer to an NMR or MRI system, the hyperpolarized molecules contain at least two nuclear spins I and S with a scalar coupling JIS, the polarization of spin I (short for 'investigated') can be determined from the asymmetry AS of the multiplet of spin S (short for 'spy'), provided perturbations due to second-order (strong coupling) effects are properly taken into account. If spin S is suitably discreet and does not affect the relaxation of spin I, this provides an elegant way of measuring spin polarizations 'on the fly' in a broad range of molecules, thus obviating the need for laborious measurements of signal intensities at thermal equilibrium. The method, dubbed Spin PolarimetrY Magnetic Resonance (SPY-MR), is illustrated for various pairs of (13)C spins (I, S) in acetate and pyruvate. Copyright © 2015 The Authors. Published by Elsevier Inc. All rights reserved.

Cross-polarization/magic-angle sample-spinning /sup 13/C NMR spectroscopic study of chlorophyll a in the solid state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, C.E.; Spencer, R.B.; Burger, V.T.

1984-01-01

Solid-state cross-polarization/magic-angle sample-spinning /sup 13/C NMR spectra have been recorded on chlorophyll a-water aggregates, methyl pyrochlorophyllide a, and methyl pyropheophorbide a. Spectra have also been collected under a decoupling regime in which resonances of certain hydrogen-bearing carbon atoms are suppressed. These observations are used to assign the solid-state spectra. 18 references, 2 figures, 1 table.

Selective Optical Addressing of Nuclear Spins through Superhyperfine Interaction in Rare-Earth Doped Solids

NASA Astrophysics Data System (ADS)

Car, B.; Veissier, L.; Louchet-Chauvet, A.; Le Gouët, J.-L.; Chanelière, T.

2018-05-01

In Er3 +:Y2SiO5 , we demonstrate the selective optical addressing of the Y89 3 + nuclear spins through their superhyperfine coupling with the Er3 + electronic spins possessing large Landé g factors. We experimentally probe the electron-nuclear spin mixing with photon echo techniques and validate our model. The site-selective optical addressing of the Y3 + nuclear spins is designed by adjusting the magnetic field strength and orientation. This constitutes an important step towards the realization of long-lived solid-state qubits optically addressed by telecom photons.

Electrically tunable dynamic nuclear spin polarization in GaAs quantum dots at zero magnetic field

NASA Astrophysics Data System (ADS)

Manca, M.; Wang, G.; Kuroda, T.; Shree, S.; Balocchi, A.; Renucci, P.; Marie, X.; Durnev, M. V.; Glazov, M. M.; Sakoda, K.; Mano, T.; Amand, T.; Urbaszek, B.

2018-04-01

In III-V semiconductor nano-structures, the electron and nuclear spin dynamics are strongly coupled. Both spin systems can be controlled optically. The nuclear spin dynamics are widely studied, but little is known about the initialization mechanisms. Here, we investigate optical pumping of carrier and nuclear spins in charge tunable GaAs dots grown on 111A substrates. We demonstrate dynamic nuclear polarization (DNP) at zero magnetic field in a single quantum dot for the positively charged exciton X+ state transition. We tune the DNP in both amplitude and sign by variation of an applied bias voltage Vg. Variation of ΔVg on the order of 100 mV changes the Overhauser splitting (nuclear spin polarization) from -30 μeV (-22%) to +10 μeV (+7%) although the X+ photoluminescence polarization does not change sign over this voltage range. This indicates that absorption in the structure and energy relaxation towards the X+ ground state might provide favourable scenarios for efficient electron-nuclear spin flip-flops, generating DNP during the first tens of ps of the X+ lifetime which is on the order of hundreds of ps. Voltage control of DNP is further confirmed in Hanle experiments.

Spin texture and magnetoroton excitations at nu=1/3.

PubMed

Groshaus, Javier G; Dujovne, Irene; Gallais, Yann; Hirjibehedin, Cyrus F; Pinczuk, Aron; Tan, Yan-Wen; Stormer, Horst; Dennis, Brian S; Pfeiffer, Loren N; West, Ken W

2008-02-01

Neutral spin texture (ST) excitations at nu=1/3 are directly observed for the first time by resonant inelastic light scattering. They are determined to involve two simultaneous spin flips. At low magnetic fields, the ST energy is below that of the magnetoroton minimum. With increasing in-plane magnetic field these mode energies cross at a critical ratio of the Zeeman and Coulomb energies of eta(c)=0.020+/-0.001. Surprisingly, the intensity of the ST mode grows with temperature in the range in which the magnetoroton modes collapse. The temperature dependence is interpreted in terms of a competition between coexisting phases supporting different excitations. We consider the role of the ST excitations in activated transport at nu=1/3.

The 13C nuclear magnetic resonance in graphite intercalation compounds

NASA Technical Reports Server (NTRS)

Tsang, T.; Resing, H. A.

1985-01-01

The (13)C NMR chemical shifts of graphite intercalation compounds were calculated. For acceptor types, the shifts come mainly from the paramagnetic (Ramsey) intra-atomic terms. They are related to the gross features of the two-dimensional band structures. The calculated anisotropy is about -140 ppm and is independent of the finer details such as charge transfer. For donor types, the carbon 2p pi orbitals are spin-polarized because of mixing with metal conduction electrons, thus there is an additional dipolar contribution which may be correlated with the electronic specific heat. The general agreement with experimental data is satisfactory.

Angstrom-Resolution Magnetic Resonance Imaging of Single Molecules via Wave-Function Fingerprints of Nuclear Spins

NASA Astrophysics Data System (ADS)

Ma, Wen-Long; Liu, Ren-Bao

2016-08-01

Single-molecule sensitivity of nuclear magnetic resonance (NMR) and angstrom resolution of magnetic resonance imaging (MRI) are the highest challenges in magnetic microscopy. Recent development in dynamical-decoupling- (DD) enhanced diamond quantum sensing has enabled single-nucleus NMR and nanoscale NMR. Similar to conventional NMR and MRI, current DD-based quantum sensing utilizes the "frequency fingerprints" of target nuclear spins. The frequency fingerprints by their nature cannot resolve different nuclear spins that have the same noise frequency or differentiate different types of correlations in nuclear-spin clusters, which limit the resolution of single-molecule MRI. Here we show that this limitation can be overcome by using "wave-function fingerprints" of target nuclear spins, which is much more sensitive than the frequency fingerprints to the weak hyperfine interaction between the targets and a sensor under resonant DD control. We demonstrate a scheme of angstrom-resolution MRI that is capable of counting and individually localizing single nuclear spins of the same frequency and characterizing the correlations in nuclear-spin clusters. A nitrogen-vacancy-center spin sensor near a diamond surface, provided that the coherence time is improved by surface engineering in the near future, may be employed to determine with angstrom resolution the positions and conformation of single molecules that are isotope labeled. The scheme in this work offers an approach to breaking the resolution limit set by the "frequency gradients" in conventional MRI and to reaching the angstrom-scale resolution.

Electrical detection of nuclear spins in organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Malissa, H.; Kavand, M.; Waters, D. P.; Lupton, J. M.; Vardeny, Z. V.; Saam, B.; Boehme, C.

2014-03-01

We present pulsed combined electrically detected electron paramagnetic and nuclear magnetic resonance experiments on MEH-PPV OLEDs. Spin dynamics in these structures are governed by hyperfine interactions between charge carriers and the surrounding hydrogen nuclei, which are abundant in these materials. Hyperfine coupling has been observed by monitoring the device current during coherent spin excitation. Electron spin echoes (ESEs) are detected by applying one additional readout pulse at the time of echo formation. This allows for the application of high-resolution spectroscopy based on ESE detection, such as electron spin echo envelope modulation (ESEEM) and electron nuclear double resonance (ENDOR) available for electrical detection schemes. We conduct electrically detected ESEEM and ENDOR experiments and show how hyperfine interactions in MEH-PPV with and without deuterated polymer side groups can be observed by device current measurements. We acknowledge support by the Department of Energy, Office of Basic Energy Sciences under Award #DE-SC0000909.

Investigation of the spin-lattice relaxation of 13CO and 13CO2 adsorbed in the metal-organic frameworks Cu3(btc)2 and Cu(3-x)Zn(x)(btc)2.

PubMed

Gul-E-Noor, Farhana; Michel, Dieter; Krautscheid, Harald; Haase, Jürgen; Bertmer, Marko

2013-07-21

The (13)C nuclear spin-lattice relaxation time of (13)CO and (13)CO2 molecules adsorbed in the metal-organic frameworks (MOFs) Cu2.97Zn0.03(btc)2 and Cu3(btc)2 is investigated over a wide range of temperatures at resonance frequencies of 75.468 and 188.62 MHz. In all cases a mono-exponential relaxation is observed, and the (13)C spin-lattice relaxation times (T1) reveal minima within the temperature range of the measurements and both frequencies. This allows us to carry out a more detailed analysis of the (13)C spin relaxation data and to consider the influence due to the spectral functions of the thermal motion. In a model-free discussion of the temperature dependence of the ratios T1 (T)∕T1,min we observe a motional mechanism that can be described by a single correlation time. In relation to the discussion of the relaxation mechanisms this can be understood in terms of dominating translational motion with mean jump distance being larger than the minimum distances between neighboring adsorption sites in the MOFs. A more detailed discussion of the jump-like motion observed here might be carried out on the basis of self-diffusion coefficients. From the present spin relaxation measurements activation energies for the local motion of the adsorbed molecules in the MOFs can be estimated to be 3.3 kJ∕mol and 2.2 kJ∕mol, for CO and CO2 molecules, respectively. Finally, our findings are compared with our recent results derived from the (13)C line shape analysis.

Theory for cross effect dynamic nuclear polarization under magic-angle spinning in solid state nuclear magnetic resonance: the importance of level crossings.

PubMed

Thurber, Kent R; Tycko, Robert

2012-08-28

We present theoretical calculations of dynamic nuclear polarization (DNP) due to the cross effect in nuclear magnetic resonance under magic-angle spinning (MAS). Using a three-spin model (two electrons and one nucleus), cross effect DNP with MAS for electron spins with a large g-anisotropy can be seen as a series of spin transitions at avoided crossings of the energy levels, with varying degrees of adiabaticity. If the electron spin-lattice relaxation time T(1e) is large relative to the MAS rotation period, the cross effect can happen as two separate events: (i) partial saturation of one electron spin by the applied microwaves as one electron spin resonance (ESR) frequency crosses the microwave frequency and (ii) flip of all three spins, when the difference of the two ESR frequencies crosses the nuclear frequency, which transfers polarization to the nuclear spin if the two electron spins have different polarizations. In addition, adiabatic level crossings at which the two ESR frequencies become equal serve to maintain non-uniform saturation across the ESR line. We present analytical results based on the Landau-Zener theory of adiabatic transitions, as well as numerical quantum mechanical calculations for the evolution of the time-dependent three-spin system. These calculations provide insight into the dependence of cross effect DNP on various experimental parameters, including MAS frequency, microwave field strength, spin relaxation rates, hyperfine and electron-electron dipole coupling strengths, and the nature of the biradical dopants.

Effects of nuclear spins on the transport properties of the edge of two-dimensional topological insulators

NASA Astrophysics Data System (ADS)

Hsu, Chen-Hsuan; Stano, Peter; Klinovaja, Jelena; Loss, Daniel

2018-03-01

The electrons in the edge channels of two-dimensional topological insulators can be described as a helical Tomonaga-Luttinger liquid. They couple to nuclear spins embedded in the host materials through the hyperfine interaction, and are therefore subject to elastic spin-flip backscattering on the nuclear spins. We investigate the nuclear-spin-induced edge resistance due to such backscattering by performing a renormalization-group analysis. Remarkably, the effect of this backscattering mechanism is stronger in a helical edge than in nonhelical channels, which are believed to be present in the trivial regime of InAs/GaSb quantum wells. In a system with sufficiently long edges, the disordered nuclear spins lead to an edge resistance which grows exponentially upon lowering the temperature. On the other hand, electrons from the edge states mediate an anisotropic Ruderman-Kittel-Kasuya-Yosida nuclear spin-spin interaction, which induces a spiral nuclear spin order below the transition temperature. We discuss the features of the spiral order, as well as its experimental signatures. In the ordered phase, we identify two backscattering mechanisms, due to charge impurities and magnons. The backscattering on charge impurities is allowed by the internally generated magnetic field, and leads to an Anderson-type localization of the edge states. The magnon-mediated backscattering results in a power-law resistance, which is suppressed at zero temperature. Overall, we find that in a sufficiently long edge the nuclear spins, whether ordered or not, suppress the edge conductance to zero as the temperature approaches zero.

Magnitude of finite-nucleus-size effects in relativistic density functional computations of indirect NMR nuclear spin-spin coupling constants.

PubMed

Autschbach, Jochen

2009-09-14

A spherical Gaussian nuclear charge distribution model has been implemented for spin-free (scalar) and two-component (spin-orbit) relativistic density functional calculations of indirect NMR nuclear spin-spin coupling (J-coupling) constants. The finite nuclear volume effects on the hyperfine integrals are quite pronounced and as a consequence they noticeably alter coupling constants involving heavy NMR nuclei such as W, Pt, Hg, Tl, and Pb. Typically, the isotropic J-couplings are reduced in magnitude by about 10 to 15 % for couplings between one of the heaviest NMR nuclei and a light atomic ligand, and even more so for couplings between two heavy atoms. For a subset of the systems studied, viz. the Hg atom, Hg(2) (2+), and Tl--X where X=Br, I, the basis set convergence of the hyperfine integrals and the coupling constants was monitored. For the Hg atom, numerical and basis set calculations of the electron density and the 1s and 6s orbital hyperfine integrals are directly compared. The coupling anisotropies of TlBr and TlI increase by about 2 % due to finite-nucleus effects.

High performance current and spin diode of atomic carbon chain between transversely symmetric ribbon electrodes.

PubMed

Dong, Yao-Jun; Wang, Xue-Feng; Yang, Shuo-Wang; Wu, Xue-Mei

2014-08-21

We demonstrate that giant current and high spin rectification ratios can be achieved in atomic carbon chain devices connected between two symmetric ferromagnetic zigzag-graphene-nanoribbon electrodes. The spin dependent transport simulation is carried out by density functional theory combined with the non-equilibrium Green's function method. It is found that the transverse symmetries of the electronic wave functions in the nanoribbons and the carbon chain are critical to the spin transport modes. In the parallel magnetization configuration of two electrodes, pure spin current is observed in both linear and nonlinear regions. However, in the antiparallel configuration, the spin-up (down) current is prohibited under the positive (negative) voltage bias, which results in a spin rectification ratio of order 10(4). When edge carbon atoms are substituted with boron atoms to suppress the edge magnetization in one of the electrodes, we obtain a diode with current rectification ratio over 10(6).

High performance current and spin diode of atomic carbon chain between transversely symmetric ribbon electrodes

PubMed Central

Dong, Yao-Jun; Wang, Xue-Feng; Yang, Shuo-Wang; Wu, Xue-Mei

2014-01-01

We demonstrate that giant current and high spin rectification ratios can be achieved in atomic carbon chain devices connected between two symmetric ferromagnetic zigzag-graphene-nanoribbon electrodes. The spin dependent transport simulation is carried out by density functional theory combined with the non-equilibrium Green's function method. It is found that the transverse symmetries of the electronic wave functions in the nanoribbons and the carbon chain are critical to the spin transport modes. In the parallel magnetization configuration of two electrodes, pure spin current is observed in both linear and nonlinear regions. However, in the antiparallel configuration, the spin-up (down) current is prohibited under the positive (negative) voltage bias, which results in a spin rectification ratio of order 104. When edge carbon atoms are substituted with boron atoms to suppress the edge magnetization in one of the electrodes, we obtain a diode with current rectification ratio over 106. PMID:25142376

Carbon-13 and proton nuclear magnetic resonance analysis of shale-derived refinery products and jet fuels and of experimental referee broadened-specification jet fuels

NASA Technical Reports Server (NTRS)

Dalling, D. K.; Bailey, B. K.; Pugmire, R. J.

1984-01-01

A proton and carbon-13 nuclear magnetic resonance (NMR) study was conducted of Ashland shale oil refinery products, experimental referee broadened-specification jet fuels, and of related isoprenoid model compounds. Supercritical fluid chromatography techniques using carbon dioxide were developed on a preparative scale, so that samples could be quantitatively separated into saturates and aromatic fractions for study by NMR. An optimized average parameter treatment was developed, and the NMR results were analyzed in terms of the resulting average parameters; formulation of model mixtures was demonstrated. Application of novel spectroscopic techniques to fuel samples was investigated.

Analysis of cocondensation of melamine and urea through carbon 13 enriched formaldehyde with C-13 nuclear magnetic resonance spectroscopy

Treesearch

Bunichiro Tomita; Chung-Yun Hse

1995-01-01

The urea-formaldehyde (UF) resins, melamine-formaldehyde (MF) resins, and melamine-ureaformaldehyde (MUF) cocondensed resins were synthesized using the labeling method with 13C enriched formaldehyde under neutral conditions and their 13C-NMR (nuclear magnetic resonance) spectra were analyzed. The remarkable down-field...

Thermal annihilation of photo-induced radicals following dynamic nuclear polarization to produce transportable frozen hyperpolarized 13C-substrates

PubMed Central

Capozzi, Andrea; Cheng, Tian; Boero, Giovanni; Roussel, Christophe; Comment, Arnaud

2017-01-01

Hyperpolarization via dynamic nuclear polarization (DNP) is pivotal for boosting magnetic resonance imaging (MRI) sensitivity and dissolution DNP can be used to perform in vivo real-time 13C MRI. The type of applications is however limited by the relatively fast decay time of the hyperpolarized spin state together with the constraint of having to polarize the 13C spins in a dedicated apparatus nearby but separated from the MRI magnet. We herein demonstrate that by polarizing 13C with photo-induced radicals, which can be subsequently annihilated using a thermalization process that maintains the sample temperature below its melting point, hyperpolarized 13C-substrates can be extracted from the DNP apparatus in the solid form, while maintaining the enhanced 13C polarization. The melting procedure necessary to transform the frozen solid into an injectable solution containing the hyperpolarized 13C-substrates can therefore be performed ex situ, up to several hours after extraction and storage of the polarized solid. PMID:28569840

Anisotropic interactions of a single spin and dark-spin spectroscopy in diamond

NASA Astrophysics Data System (ADS)

Epstein, R. J.; Mendoza, F. M.; Kato, Y. K.; Awschalom, D. D.

2005-11-01

Experiments on single nitrogen-vacancy (N-V) centres in diamond, which include electron spin resonance, Rabi oscillations, single-shot spin readout and two-qubit operations with a nearby13C nuclear spin, show the potential of this spin system for solid-state quantum information processing. Moreover, N-V centre ensembles can have spin-coherence times exceeding 50 μs at room temperature. We have developed an angle-resolved magneto-photoluminescence microscope apparatus to investigate the anisotropic electron-spin interactions of single N-V centres at room temperature. We observe negative peaks in the photoluminescence as a function of both magnetic-field magnitude and angle that are explained by coherent spin precession and anisotropic relaxation at spin-level anti-crossings. In addition, precise field alignment unmasks the resonant coupling to neighbouring `dark' nitrogen spins, otherwise undetected by photoluminescence. These results demonstrate the capability of our spectroscopic technique for measuring small numbers of dark spins by means of a single bright spin under ambient conditions.

Optimization of 13C dynamic nuclear polarization: isotopic labeling of free radicals

NASA Astrophysics Data System (ADS)

Niedbalski, Peter; Parish, Christopher; Kiswandi, Andhika; Lumata, Lloyd

Dynamic nuclear polarization (DNP) is a physics technique that amplifies the nuclear magnetic resonance (NMR) signals by transferring the high polarization of the electrons to the nuclear spins. Thus, the choice of free radical is crucial in DNP as it can directly affect the NMR signal enhancement levels, typically on the order of several thousand-fold in the liquid-state. In this study, we have investigated the efficiency of four variants of the well-known 4-oxo-TEMPO radical (normal 4-oxo-TEMPO plus its 15N-enriched and/or perdeuterated variants) for use in DNP of an important metabolic tracer [1-13C]acetate. Though the variants have significant differences in electron paramagnetic resonance (EPR) spectra, we have found that changing the composition of the TEMPO radical through deuteration or 15N doping yields no significant difference in 13C DNP efficiency at 3.35 T and 1.2 K. On the other hand, deuteration of the solvent causes a significant increase of 13C polarization that is consistent over all the 4-oxo-TEMPO variants. These findings are consistent with the thermal mixing model of DNP. This work is supported by US Dept of Defense Award No. W81XWH-14-1-0048 and the Robert A. Welch Foundation Grant No. AT-1877.

Optical Polarization of Nuclear Spins in Silicon Carbide

NASA Astrophysics Data System (ADS)

Falk, Abram L.; Klimov, Paul V.; Ivády, Viktor; Szász, Krisztián; Christle, David J.; Koehl, William F.; Gali, Ádám; Awschalom, David D.

2015-06-01

We demonstrate optically pumped dynamic nuclear polarization of 29Si nuclear spins that are strongly coupled to paramagnetic color centers in 4 H - and 6 H -SiC. The 9 9 % ±1 % degree of polarization that we observe at room temperature corresponds to an effective nuclear temperature of 5 μ K . By combining ab initio theory with the experimental identification of the color centers' optically excited states, we quantitatively model how the polarization derives from hyperfine-mediated level anticrossings. These results lay a foundation for SiC-based quantum memories, nuclear gyroscopes, and hyperpolarized probes for magnetic resonance imaging.

Phonon-mediated nuclear spin relaxation in H2O

NASA Astrophysics Data System (ADS)

Yamakawa, Koichiro; Azami, Shinya; Arakawa, Ichiro

2017-03-01

A theoretical model of the phonon-mediated nuclear spin relaxation in H2O trapped by cryomatrices has been established for the first time. In order to test the validity of this model, we measured infrared spectra of H2O trapped in solid Ar, which showed absorption peaks due to rovibrational transitions of ortho- and para-H2O in the spectral region of the bending vibration. We monitored the time evolution of the spectra and analyzed the rotational relaxation associated with the nuclear spin flip to obtain the relaxation rates of H2O at temperatures of 5-15 K. Temperature dependence of the rate is discussed in terms of the devised model.

Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nozirov, Farhod, E-mail: teobaldk@gmail.com, E-mail: farhod.nozirov@gmail.com; Stachów, Michał, E-mail: michal.stachow@gmail.com; Kupka, Teobald, E-mail: teobaldk@gmail.com, E-mail: farhod.nozirov@gmail.com

2014-04-14

A theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis- and trans-1,2-difluoroethylenes is reported. The results obtained using density functional theory (DFT) combined with large basis sets and gauge-independent atomic orbital calculations were critically compared with experiment and conventional, higher level correlated electronic structure methods. Accurate structural, vibrational, and NMR parameters of difluoroethylenes were obtained using several density functionals combined with dedicated basis sets. B3LYP/6-311++G(3df,2pd) optimized structures of difluoroethylenes closely reproduced experimental geometries and earlier reported benchmark coupled cluster results, while BLYP/6-311++G(3df,2pd) produced accurate harmonic vibrational frequencies. The most accurate vibrations were obtained using B3LYP/6-311++G(3df,2pd)more » with correction for anharmonicity. Becke half and half (BHandH) density functional predicted more accurate {sup 19}F isotropic shieldings and van Voorhis and Scuseria's τ-dependent gradient-corrected correlation functional yielded better carbon shieldings than B3LYP. A surprisingly good performance of Hartree-Fock (HF) method in predicting nuclear shieldings in these molecules was observed. Inclusion of zero-point vibrational correction markedly improved agreement with experiment for nuclear shieldings calculated by HF, MP2, CCSD, and CCSD(T) methods but worsened the DFT results. The threefold improvement in accuracy when predicting {sup 2}J(FF) in 1,1-difluoroethylene for BHandH density functional compared to B3LYP was observed (the deviations from experiment were −46 vs. −115 Hz)« less

Construction and 13C NMR signal-amplification efficiency of a dynamic nuclear polarizer at 6.4 T and 1.4 K

NASA Astrophysics Data System (ADS)

Kiswandhi, Andhika; Niedbalski, Peter; Parish, Christopher; Ferguson, Sarah; Taylor, David; McDonald, George; Lumata, Lloyd

Dissolution dynamic nuclear polarization (DNP) is a rapidly emerging technique in biomedical and metabolic imaging since it amplifies the liquid-state nuclear magnetic resonance (NMR) and imaging (MRI) signals by >10,000-fold. Originally used in nuclear scattering experiments, DNP works by creating a non-Boltzmann nuclear spin distribution by transferring the high electron (γ = 28,000 MHz/T) thermal polarization to the nuclear spins via microwave irradiation of the sample at high magnetic field and low temperature. A dissolution device is used to rapidly dissolve the frozen sample and consequently produces an injectable ``hyperpolarized'' liquid at physiologically-tolerable temperature. Here we report the construction and performance evaluation of a dissolution DNP hyperpolarizer at 6.4 T and 1.4 K using a continuous-flow cryostat. The solid and liquid-state 13C NMR signal enhancement levels of 13C acetate samples doped with trityl OX063 and 4-oxo-TEMPO free radicals will be discussed and compared with the results from the 3.35 T commercial hyperpolarizer. This work is supported by US Dept of Defense Award No. W81XWH-14-1-0048 and Robert A. Welch Foundation Grant No. AT-1877.

Nuclear spin warm up in bulk n -GaAs

NASA Astrophysics Data System (ADS)

Kotur, M.; Dzhioev, R. I.; Vladimirova, M.; Jouault, B.; Korenev, V. L.; Kavokin, K. V.

2016-08-01

We show that the spin-lattice relaxation in n -type insulating GaAs is dramatically accelerated at low magnetic fields. The origin of this effect, which cannot be explained in terms of well-known diffusion-limited hyperfine relaxation, is found in the quadrupole relaxation, induced by fluctuating donor charges. Therefore, quadrupole relaxation, which governs low field nuclear spin relaxation in semiconductor quantum dots, but was so far supposed to be harmless to bulk nuclei spins in the absence of optical pumping, can be studied and harnessed in the much simpler model environment of n -GaAs bulk crystal.

Characterization of oil shale, isolated kerogen, and post-pyrolysis residues using advanced 13 solid-state nuclear magnetic resonance spectroscopy

USGS Publications Warehouse

Cao, Xiaoyan; Birdwell, Justin E.; Chappell, Mark A.; Li, Yuan; Pignatello, Joseph J.; Mao, Jingdong

2013-01-01

Characterization of oil shale kerogen and organic residues remaining in postpyrolysis spent shale is critical to the understanding of the oil generation process and approaches to dealing with issues related to spent shale. The chemical structure of organic matter in raw oil shale and spent shale samples was examined in this study using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Oil shale was collected from Mahogany zone outcrops in the Piceance Basin. Five samples were analyzed: (1) raw oil shale, (2) isolated kerogen, (3) oil shale extracted with chloroform, (4) oil shale retorted in an open system at 500°C to mimic surface retorting, and (5) oil shale retorted in a closed system at 360°C to simulate in-situ retorting. The NMR methods applied included quantitative direct polarization with magic-angle spinning at 13 kHz, cross polarization with total sideband suppression, dipolar dephasing, CHn selection, 13C chemical shift anisotropy filtering, and 1H-13C long-range recoupled dipolar dephasing. The NMR results showed that, relative to the raw oil shale, (1) bitumen extraction and kerogen isolation by demineralization removed some oxygen-containing and alkyl moieties; (2) unpyrolyzed samples had low aromatic condensation; (3) oil shale pyrolysis removed aliphatic moieties, leaving behind residues enriched in aromatic carbon; and (4) oil shale retorted in an open system at 500°C contained larger aromatic clusters and more protonated aromatic moieties than oil shale retorted in a closed system at 360°C, which contained more total aromatic carbon with a wide range of cluster sizes.

Spin-orbit coupling effect on structural and magnetic properties of ConRh13-n (n = 0-13) clusters

NASA Astrophysics Data System (ADS)

Bai, Xi; Lv, Jin; Zhang, Fu-Qiang; Jia, Jian-Feng; Wu, Hai-Shun

2018-04-01

The effect of spin-orbit interaction on the structures and magnetism of ConRh13-n (n = 0-13) clusters have been systematically investigated by using the spin-orbit coupling (SOC) implementation of the density functional theory (DFT). The results calculated without SOC (NSOC) show that Rh13 prefers the double simple-cubic configuration, and icosahedron is the favorable structure for n = 1-9, while n ≥ 10, clusters favor the hexagonal bilayer structure. The inclusion of SOC in calculation does not change the geometries of clusters. Compared with that in NSOC calculation, although the binding energy per atom in clusters with same composition decreases in SOC calculation, the relative stability of clusters with different compositions does not change. An interesting result is that the spin moments of clusters for n = 1-9 are almost constant (21 μB). Spin-orbit interaction recovers orbital moment and its anisotropy by removing crystal-field effect in calculation. The destruction of bonding symmetry and relaxation of bonding account for high anisotropies of orbital moments in Co11Rh2 and CoRh12 clusters. With atomic composition (Co/Rh) around 4/9-5/8 and 9/4, the Co-Rh clusters exhibit high magnetic anisotropy energies.

Protocol for generating multiphoton entangled states from quantum dots in the presence of nuclear spin fluctuations

NASA Astrophysics Data System (ADS)

Denning, Emil V.; Iles-Smith, Jake; McCutcheon, Dara P. S.; Mork, Jesper

2017-12-01

Multiphoton entangled states are a crucial resource for many applications in quantum information science. Semiconductor quantum dots offer a promising route to generate such states by mediating photon-photon correlations via a confined electron spin, but dephasing caused by the host nuclear spin environment typically limits coherence (and hence entanglement) between photons to the spin T2* time of a few nanoseconds. We propose a protocol for the deterministic generation of multiphoton entangled states that is inherently robust against the dominating slow nuclear spin environment fluctuations, meaning that coherence and entanglement is instead limited only by the much longer spin T2 time of microseconds. Unlike previous protocols, the present scheme allows for the generation of very low error probability polarization encoded three-photon GHZ states and larger entangled states, without the need for spin echo or nuclear spin calming techniques.

Molecular motions of [Beta]-carotene and a carotenoporphyrin dyad in solution. A carbon-13 NMR spin-lattice relaxation time study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, S.; Swindle, S.L.; Smith, S.K.

1995-03-09

Analysis of [sup 13]C NMR spin-lattice relaxation times (T[sub 1]) yields information concerning both overall tumbling of molecules in solution and internal rotations about single bonds. Relaxation time and nuclear Overhauser effect data have been obtained for [Beta]-carotene and two related molecules, squalane and squalene, for zinc meso-tetraphenylporphyrin, and for a dyad consisting of a porphyrin covalently linked to a carotenoid polyene through a trimethylene bridge. Squalane and squalene, which lack conjugated double bonds, behave essentially as limp string, with internal rotations at least as rapid as overall isotropic tumbling motions. In contrast, [Beta]-carotene reorients as a rigid rod, withmore » internal motions which are too slow to affect relaxation times. Modeling it as an anisotropic rotor yields a rotational diffusion coefficient for motion about the major axis which is 14 times larger than that for rotation about axes perpendicular to that axis. The porphyrin reorients more nearly isotropically and features internal librational motions about the single bonds to the phenyl groups. The relaxation time data for the carotenoporphyrin are consistent with internal motions similar to those of a medieval military flail. 31 refs., 3 figs., 5 tabs.« less

Separation and conversion dynamics of nuclear-spin isomers of gaseous methanol

PubMed Central

Sun, Zhen-Dong; Ge, Meihua; Zheng, Yujun

2015-01-01

All symmetrical molecules with non-zero nuclear spin exist in nature as nuclear-spin isomers (NSIs). However, owing to the lack of experimental information, knowledge is rare about interconversions of NSIs of gaseous molecules with torsional symmetry. Here we report our separation and conversion observations on NSI-torsion-specific transition systems of gaseous methanol from a light-induced drift experiment involving partially spatial separation of the ortho and para isomers. We find that vibrationally excited molecules of the methanol spin isomer have a smaller collision cross-section than their ground-state counterparts. Interconversion of the enriched ortho isomer with the para isomer, which is generally considered improbable, has been quantitatively studied by sensitive detections of the spectral intensities. Rather counterintuitively, this reveals that the interconversion is inhibited with increasing pressure. Our results suggest that the spin conversion mechanism in methanol is via a quantum relaxation process with the quantum Zeno effect induced by molecular collisions. PMID:25880882

Prostaglandin H synthase-catalyzed oxidation of all-trans- and 13-cis-retinoic acid to carbon-centered and peroxyl radical intermediates.

PubMed

Freyaldenhoven, M A; Lloyd, R V; Samokyszyn, V M

1996-06-01

Due to the importance of all-trans-retinoic acid (RA) in the treatment of various dermatological conditions and the wide distribution of prostaglandin H synthase (PGHS) in tissues, we have further examined the mechanisms involved in the hydroperoxide-dependent cooxidation of RA and its isomer, 13-cis-retinoic acid ((13Z)-RA), by PGHS. Hydroperoxide-dependent, PGHS-catalyzed oxidation of RA and (13Z)-RA was shown to form free radical adducts, using electron spin resonance (ESR) spin trapping techniques and 5-phenyl-4-penten-1-yl hydroperoxide (PPHP) or 13-hydroperoxy-9-cis-11-trans-octadecadienoic acid (13-OOH-18:2) as hydroperoxide substrates. Utilization of the spin trap alpha-phenyl-N-tert-butylnitrone (PBN) resulted in the detection of (13Z)-RA-PBN and RA-PBN adducts whose spectra were characterized by hyperfine coupling constants of aH = 4.16/aN = 15.69 and aH = 3.01/aN =15.92, respectively. Identical experiments under anaerobic conditions were carried out using the spin trap 2-methyl-2-nitrosopropane (NtB) which yielded nitroxide adducts whose spectra were characterized by a triplet of doublets with values of aH = 3.49/aN = 15.84 for the (13Z)-RA adduct and aH = 3.49/aN = 15.88 for the RA adduct. These results are indicative of secondary carbon-centered radical formation. We also used (+)-benzo[a]pyrene 7(S),8(S)-dihydrodiol ((+)-BP-7,8-diol) as a peroxyl radical probe. The results demonstrated the formation of (+)-BP-7,8-diol-derived tetrols, with the trans-anti tetrol representing the major oxidation product in systems undergoing PPHP-dependent, PGHS-catalyzed oxidation of (13Z)-RA or RA. These results are consistent with the formation of peroxyl radicals in these systems. In all experiments, the (13Z)-RA isomer appeared to be a better substrate for the enzyme compared to the all-trans isomer. Collectively these results provide further evidence to support the previously proposed mechanism for retinoid oxidation by PGHS involving the intermediacy of C4 carbon

Effect of electron spin-spin interaction on level crossings and spin flips in a spin-triplet system

NASA Astrophysics Data System (ADS)

Jia, Wei; Hu, Fang-Qi; Wu, Ning; Zhao, Qing

2017-12-01

We study level crossings and spin flips in a system consisting of a spin-1 (an electron spin triplet) coupled to a nuclear spin of arbitrary size K , in the presence of a uniform magnetic field and the electron spin-spin interaction within the triplet. Through an analytical diagonalization based on the SU (3 ) Lie algebra, we find that the electron spin-spin interaction not only removes the curious degeneracy which appears in the absence of the interaction, but also produces some level anticrossings (LACs) for strong interactions. The real-time dynamics of the system shows that periodic spin flips occur at the LACs for arbitrary K , which might provide an option for nuclear or electron spin polarization.

Nuclear-spin-independent short-range three-body physics in ultracold atoms.

PubMed

Gross, Noam; Shotan, Zav; Kokkelmans, Servaas; Khaykovich, Lev

2010-09-03

We investigate three-body recombination loss across a Feshbach resonance in a gas of ultracold 7Li atoms prepared in the absolute ground state and perform a comparison with previously reported results of a different nuclear-spin state [N. Gross, Phys. Rev. Lett. 103, 163202 (2009)]. We extend the previously reported universality in three-body recombination loss across a Feshbach resonance to the absolute ground state. We show that the positions and widths of recombination minima and Efimov resonances are identical for both states which indicates that the short-range physics is nuclear-spin independent.

Quantum information generation, storage and transmission based on nuclear spins

NASA Astrophysics Data System (ADS)

Zaharov, V. V.; Makarov, V. I.

2018-05-01

A new approach to quantum information generation, storage and transmission is proposed. It is shown that quantum information generation and storage using an ensemble of N electron spins encounter unresolvable implementation problems (at least at the present time). As an alternative implementation we discuss two promising radical systems, one with N equivalent nuclear spins and another with N nonequivalent nuclear spins. Detailed analysis shows that only the radical system containing N nonequivalent nuclei is perfectly matched for quantum information generation, storage and transmission. We develop a procedure based on pulsed electron paramagnetic resonance (EPR) and we apply it to the radical system with the set of nonequivalent nuclei. The resulting EPR spectrum contains 2N transition lines, where N is the number of the atoms with the nuclear spin 1/2, and each of these lines may be encoded with a determined qudit sequence. For encoding the EPR lines we propose to submit the radical system to two magnetic pulses in the direction perpendicular to the z axis of the reference frame. As a result, the radical system impulse response may be measured, stored and transmitted through the communications channel. Confirming our development, the ab initio analysis of the system with three anion radicals was done showing matching between the simulations and the theoretical predictions. The developed method may be easily adapted for quantum information generation, storage, processing and transmission in quantum computing and quantum communications applications.

Electron Spin Relaxation Rates for High-Spin Fe(III) in Iron Transferrin Carbonate and Iron Transferrin Oxalate

PubMed Central

Gaffney, Betty Jean; Eaton, Gareth R.; Eaton*, Sandra S.

2005-01-01

To optimize simulations of CW EPR spectra for high-spin Fe(III) with zero-field splitting comparable to the EPR quantum, information is needed on the factors that contribute to the line shapes and line widths. Continuous wave electron paramagnetic resonance (EPR) spectra obtained for iron transferrin carbonate from 4 to 150 K and for iron transferrin oxalate from 4 to 100 K did not exhibit significant temperature dependence of the line shape, which suggested that the line shapes were not relaxation determined. To obtain direct information concerning the electron spin relaxation rates, electron spin echo and inversion recovery EPR were used to measure T1 and Tm for the high-spin Fe(III) in iron transferrin carbonate and iron transferrin oxalate between 5 and 20–30 K. For comparison with the data for the transferrin complexes, relaxation times were obtained for tris(oxalato)ferrate(III). The relaxation rates are similar for the three complexes and do not exhibit a strong dependence on position in the spectrum. Extrapolation of the observed temperature dependence of the relaxation rates to higher temperatures gives values consistent with the conclusion that the CW line shapes are not relaxation determined up to 150 K. PMID:16429607

Nuclear spin dependence of time reversal invariance violating effects in neutron scattering

NASA Astrophysics Data System (ADS)

Gudkov, Vladimir; Shimizu, Hirohiko M.

2018-06-01

The spin structure of parity violating and time reversal invariance violating effects in neutron scattering is discussed. The explicit relations between these effects are presented in terms of functions nuclear spins and neutron partial widths of p -wave resonances.

Coherent manipulation of non-thermal spin order in optical nuclear polarization experiments

NASA Astrophysics Data System (ADS)

Buntkowsky, Gerd; Ivanov, Konstantin L.; Zimmermann, Herbert; Vieth, Hans-Martin

2017-03-01

Time resolved measurements of Optical Nuclear Polarization (ONP) have been performed on hyperpolarized triplet states in molecular crystals created by light excitation. Transfer of the initial electron polarization to nuclear spins has been studied in the presence of radiofrequency excitation; the experiments have been performed with different pulse sequences using different doped molecular systems. The experimental results clearly demonstrate the dominant role of coherent mechanisms of spin order transfer, which manifest themselves in well pronounced oscillations. These oscillations are of two types, precessions and nutations, having characteristic frequencies, which are the same for the different molecular systems and the pulse sequences applied. Hence, precessions and nutations constitute a general feature of polarization transfer in ONP experiments. In general, coherent manipulation of spin order transfer creates a powerful resource for improving the performance of the ONP method, which paves the way to strong signal enhancement in nuclear magnetic resonance.

Nuclear spin dependence of time reversal invariance violating effects in neutron scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gudkov, Vladimir; Shimizu, Hirohiko M.

In this study, the spin structure of parity violating and time reversal invariance violating effects in neutron scattering is discussed. The explicit relations between these effects are presented in terms of functions nuclear spins and neutron partial widths of p-wave resonances.

Nuclear spin dependence of time reversal invariance violating effects in neutron scattering

DOE PAGES

Gudkov, Vladimir; Shimizu, Hirohiko M.

2018-06-11

In this study, the spin structure of parity violating and time reversal invariance violating effects in neutron scattering is discussed. The explicit relations between these effects are presented in terms of functions nuclear spins and neutron partial widths of p-wave resonances.

Computation of indirect nuclear spin-spin couplings with reduced complexity in pure and hybrid density functional approximations.

PubMed

Luenser, Arne; Kussmann, Jörg; Ochsenfeld, Christian

2016-09-28

We present a (sub)linear-scaling algorithm to determine indirect nuclear spin-spin coupling constants at the Hartree-Fock and Kohn-Sham density functional levels of theory. Employing efficient integral algorithms and sparse algebra routines, an overall (sub)linear scaling behavior can be obtained for systems with a non-vanishing HOMO-LUMO gap. Calculations on systems with over 1000 atoms and 20 000 basis functions illustrate the performance and accuracy of our reference implementation. Specifically, we demonstrate that linear algebra dominates the runtime of conventional algorithms for 10 000 basis functions and above. Attainable speedups of our method exceed 6 × in total runtime and 10 × in the linear algebra steps for the tested systems. Furthermore, a convergence study of spin-spin couplings of an aminopyrazole peptide upon inclusion of the water environment is presented: using the new method it is shown that large solvent spheres are necessary to converge spin-spin coupling values.

Solid effect in magic angle spinning dynamic nuclear polarization

NASA Astrophysics Data System (ADS)

Corzilius, Björn; Smith, Albert A.; Griffin, Robert G.

2012-08-01

For over five decades, the solid effect (SE) has been heavily utilized as a mechanism for performing dynamic nuclear polarization (DNP). Nevertheless, it has not found widespread application in contemporary, high magnetic field DNP experiments because SE enhancements display an ω _0 ^{ - 2} field dependence. In particular, for nominally forbidden zero and double quantum SE transitions to be partially allowed, it is necessary for mixing of adjacent nuclear spin states to occur, and this leads to the observed field dependence. However, recently we have improved our instrumentation and report here an enhancement of ɛ = 91 obtained with the organic radical trityl (OX063) in magic angle spinning experiments performed at 5 T and 80 K. This is a factor of 6-7 higher than previous values in the literature under similar conditions. Because the solid effect depends strongly on the microwave field strength, we attribute this large enhancement to larger microwave field strengths inside the sample volume, achieved with more efficient coupling of the gyrotron to the sample chamber. In addition, we develop a theoretical model to explain the dependence of the buildup rate of enhanced nuclear polarization and the steady-state enhancement on the microwave power. Buildup times and enhancements were measured as a function of 1H concentration for both trityl and Gd-DOTA. Comparison of the results indicates that for trityl the initial polarization step is the slower, rate-determining step. However, for Gd-DOTA the spread of nuclear polarization via homonuclear 1H spin diffusion is rate-limiting. Finally, we discuss the applicability of the solid effect at fields > 5 T and the requirements to address the unfavorable field dependence of the solid effect.

The determination of the in situ structure by nuclear spin contrast variation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stuhrmann, H.B.; Nierhaus, K.H.

1994-12-31

Polarized neutron scattering from polarized nuclear spins in hydrogenous substances opens a new way of contrast variation. The enhanced contrast due to proton spin polarization was used for the in situ structure determination of tRNA of the functional complex of the E.coli ribosome.

Microtesla SABRE enables 10% nitrogen-15 nuclear spin polarization.

PubMed

Theis, Thomas; Truong, Milton L; Coffey, Aaron M; Shchepin, Roman V; Waddell, Kevin W; Shi, Fan; Goodson, Boyd M; Warren, Warren S; Chekmenev, Eduard Y

2015-02-04

Parahydrogen is demonstrated to efficiently transfer its nuclear spin hyperpolarization to nitrogen-15 in pyridine and nicotinamide (vitamin B(3) amide) by conducting "signal amplification by reversible exchange" (SABRE) at microtesla fields within a magnetic shield. Following transfer of the sample from the magnetic shield chamber to a conventional NMR spectrometer, the (15)N NMR signals for these molecules are enhanced by ∼30,000- and ∼20,000-fold at 9.4 T, corresponding to ∼10% and ∼7% nuclear spin polarization, respectively. This method, dubbed "SABRE in shield enables alignment transfer to heteronuclei" or "SABRE-SHEATH", promises to be a simple, cost-effective way to hyperpolarize heteronuclei. It may be particularly useful for in vivo applications because of longer hyperpolarization lifetimes, lack of background signal, and facile chemical-shift discrimination of different species.

Microtesla SABRE Enables 10% Nitrogen-15 Nuclear Spin Polarization

PubMed Central

2016-01-01

Parahydrogen is demonstrated to efficiently transfer its nuclear spin hyperpolarization to nitrogen-15 in pyridine and nicotinamide (vitamin B3 amide) by conducting “signal amplification by reversible exchange” (SABRE) at microtesla fields within a magnetic shield. Following transfer of the sample from the magnetic shield chamber to a conventional NMR spectrometer, the 15N NMR signals for these molecules are enhanced by ∼30,000- and ∼20,000-fold at 9.4 T, corresponding to ∼10% and ∼7% nuclear spin polarization, respectively. This method, dubbed “SABRE in shield enables alignment transfer to heteronuclei” or “SABRE-SHEATH”, promises to be a simple, cost-effective way to hyperpolarize heteronuclei. It may be particularly useful for in vivo applications because of longer hyperpolarization lifetimes, lack of background signal, and facile chemical-shift discrimination of different species. PMID:25583142

Calibration of an analyzing magnet using the 12C(d, p0)13C nuclear reaction with a thick carbon target

NASA Astrophysics Data System (ADS)

Andrade, E.; Canto, C. E.; Rocha, M. F.

2017-09-01

The absolute energy of an ion beam produced by an accelerator is usually determined by an electrostatic or magnetic analyzer, which in turn must be calibrated. Various methods for accelerator energy calibration are extensively reported in the literature, like nuclear reaction resonances, neutron threshold, and time of flight, among others. This work reports on a simple method to calibrate the magnet associated to a vertical 5.5 MV Van de Graaff accelerator. The method is based on bombarding with deuteron beams a thick carbon target and measuring with a surface barrier detector the particle energy spectra produced. The analyzer magnetic field is measured for each spectrum and the beam energy is deduced by the best fit of the simulation of the spectrum with the SIMNRA code that includes 12C(d,p0)13C nuclear cross sections.

Protecting solid-state spins from a strongly coupled environment

NASA Astrophysics Data System (ADS)

Chen, Mo; Calvin Sun, Won Kyu; Saha, Kasturi; Jaskula, Jean-Christophe; Cappellaro, Paola

2018-06-01

Quantum memories are critical for solid-state quantum computing devices and a good quantum memory requires both long storage time and fast read/write operations. A promising system is the nitrogen-vacancy (NV) center in diamond, where the NV electronic spin serves as the computing qubit and a nearby nuclear spin as the memory qubit. Previous works used remote, weakly coupled 13C nuclear spins, trading read/write speed for long storage time. Here we focus instead on the intrinsic strongly coupled 14N nuclear spin. We first quantitatively understand its decoherence mechanism, identifying as its source the electronic spin that acts as a quantum fluctuator. We then propose a scheme to protect the quantum memory from the fluctuating noise by applying dynamical decoupling on the environment itself. We demonstrate a factor of 3 enhancement of the storage time in a proof-of-principle experiment, showing the potential for a quantum memory that combines fast operation with long coherence time.

Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

USGS Publications Warehouse

Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

2009-01-01

The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated

Electron spin resonance investigations of /sup 11/B/sup 12/C, /sup 11/B/sup 13/C, and /sup 10/B/sup 12/C in neon, argon, and krypton matrices at 4 K: Comparison with theoretical results

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knight L.B. Jr.; Cobranchi, S.T.; Petty, J.T.

1989-01-15

The first spectroscopic study of the diatomic radical BC is reported which confirms previous theoretical predictions of a /sup 4/summation/sup -/ electronic ground state. The nuclear hyperfine interactions (A tensors) obtained for /sup 11/B, /sup 10/B, and /sup 13/C from the electron spin resonance (ESR) measurements are compared with extensive ab initio CI calculations. The BC molecule is one of the first examples of a small high spin radical for such an in-depth experimental--theoretical comparison. The electronic structure of BC obtained from an analysis of the nuclear hyperfine interaction (hfi) is compared to that obtained from a Mulliken-type population analysismore » conducted on a CI wave function which yields A/sub iso/ and A/sub dip/ results in good agreement with the observed values. The BC radical was generated by the laser vaporization of a boron--carbon mixture and trapped in neon, argon, and krypton matrices at 4 K for a complete ESR characterization. The magnetic parameters (MHz) obtained for /sup 11/B/sup 13/C in solid neon are: g/sub parallel/ = 2.0015(3); g/sub perpendicular/ = 2.0020(3); D(zfs) = 1701(2); /sup 11/B: chemically bondA/sub parallel/chemically bond = 100(1); chemically bondA/sub perpendicular/chemically bond = 79(1); /sup 13/C: chemically bondA/sub parallel/chemically bond = 5(2) and chemically bondA/sub perpendicular/chemically bond = 15(1). Based on comparison with the theoretical results, the most likely choice of signs is that all A values are positive.« less

13 C dynamic nuclear polarization using isotopically enriched 4-oxo-TEMPO free radicals.

PubMed

Niedbalski, Peter; Parish, Christopher; Kiswandhi, Andhika; Lumata, Lloyd

2016-12-01

The nitroxide-based free radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) is a widely used polarizing agent in NMR signal amplification via dissolution dynamic nuclear polarization (DNP). In this study, we have thoroughly investigated the effects of 15 N and/or 2 H isotopic labeling of 4-oxo-TEMPO free radical on 13 C DNP of 3 M [1- 13 C] sodium acetate samples in 1 : 1 v/v glycerol : water at 3.35 T and 1.2 K. Four variants of this free radical were used for 13 C DNP: 4-oxo-TEMPO, 4-oxo-TEMPO- 15 N, 4-oxo-TEMPO-d 16 and 4-oxo-TEMPO- 15 N,d 16 . Our results indicate that, despite the striking differences seen in the electron spin resonance (ESR) spectral features, the 13 C DNP efficiency of these 15 N and/or 2 H-enriched 4-oxo-TEMPO free radicals are relatively the same compared with 13 C DNP performance of the regular 4-oxo-TEMPO. Furthermore, when fully deuterated glassing solvents were used, the 13 C DNP signals of these samples all doubled in the same manner, and the 13 C polarization buildup was faster by a factor of 2 for all samples. The data here suggest that the hyperfine coupling contributions of these isotopically enriched 4-oxo-TEMPO free radicals have negligible effects on the 13 C DNP efficiency at 3.35 T and 1.2 K. These results are discussed in light of the spin temperature model of DNP. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Nuclear-spin optical rotation in xenon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savukov, Igor Mykhaylovich

We report that the nuclear-spin optical rotation (NSOR) effect, which has potential applications in correlated nuclear-spin-resonance optical spectroscopy, has previously been explored experimentally and theoretically in liquid Xe. Calculations of the Xe NSOR constant are very challenging because the result is sensitive to correlations, relativistic effects, and the choice of basis, with strong cancellation between contributions from lowest and remaining states. The relativistic configuration-interaction many-body-theory approach, presented here, is promising because this approach has been successful in predicting various properties of noble-gas atoms, such as energies, oscillator strengths (OSs), Verdet constants, and photoionization cross sections. However, correlations become stronger alongmore » the sequence of noble-gas atoms and the theoretical accuracy in Xe is not as high as, for example, in neon and argon. To improve the accuracy of the Xe Verdet and NSOR constants, which are calculated as explicit sums over the excited states, theoretical values for the several lowest levels are replaced with empirical values of energies, OSs, and hyperfine structure constants. We found that the Xe Verdet constant is in excellent agreement with accurate measurements. To take into account liquid effects, empirical data for energy shifts were also used to correct the NSOR constant. In conclusion, the resulting Xe NSOR constant is in a good agreement with experiment, although the liquid-state effect is treated quite approximately.« less

Nuclear-spin optical rotation in xenon

DOE PAGES

Savukov, Igor Mykhaylovich

2015-10-29

We report that the nuclear-spin optical rotation (NSOR) effect, which has potential applications in correlated nuclear-spin-resonance optical spectroscopy, has previously been explored experimentally and theoretically in liquid Xe. Calculations of the Xe NSOR constant are very challenging because the result is sensitive to correlations, relativistic effects, and the choice of basis, with strong cancellation between contributions from lowest and remaining states. The relativistic configuration-interaction many-body-theory approach, presented here, is promising because this approach has been successful in predicting various properties of noble-gas atoms, such as energies, oscillator strengths (OSs), Verdet constants, and photoionization cross sections. However, correlations become stronger alongmore » the sequence of noble-gas atoms and the theoretical accuracy in Xe is not as high as, for example, in neon and argon. To improve the accuracy of the Xe Verdet and NSOR constants, which are calculated as explicit sums over the excited states, theoretical values for the several lowest levels are replaced with empirical values of energies, OSs, and hyperfine structure constants. We found that the Xe Verdet constant is in excellent agreement with accurate measurements. To take into account liquid effects, empirical data for energy shifts were also used to correct the NSOR constant. In conclusion, the resulting Xe NSOR constant is in a good agreement with experiment, although the liquid-state effect is treated quite approximately.« less

A carbon-13 and proton nuclear magnetic resonance study of some experimental referee broadened-specification /ERBS/ turbine fuels

NASA Technical Reports Server (NTRS)

Dalling, D. K.; Pugmire, R. J.

1982-01-01

Preliminary results of a nuclear magnetic resonance (NMR) spectroscopy study of alternative jet fuels are presented. A referee broadened-specification (ERBS) aviation turbine fuel, a mixture of 65 percent traditional kerosene with 35 percent hydrotreated catalytic gas oil (HCGO) containing 12.8 percent hydrogen, and fuels of lower hydrogen content created by blending the latter with a mixture of HCGO and xylene bottoms were studied. The various samples were examined by carbon-13 and proton NMR at high field strength, and the resulting spectra are shown. In the proton spectrum of the 12.8 percent hydrogen fuel, no prominent single species is seen while for the blending stock, many individual lines are apparent. The ERBS fuels were fractionated by high-performance liquid chromatography and the resulting fractions analyzed by NMR. The species found are identified.

Exploring Localization in Nuclear Spin Chains

NASA Astrophysics Data System (ADS)

Wei, Ken Xuan; Ramanathan, Chandrasekhar; Cappellaro, Paola

2018-02-01

Characterizing out-of-equilibrium many-body dynamics is a complex but crucial task for quantum applications and understanding fundamental phenomena. A central question is the role of localization in quenching thermalization in many-body systems and whether such localization survives in the presence of interactions. Probing this question in real systems necessitates the development of an experimentally measurable metric that can distinguish between different types of localization. While it is known that the localized phase of interacting systems [many-body localization (MBL)] exhibits a long-time logarithmic growth in entanglement entropy that distinguishes it from the noninteracting case of Anderson localization (AL), entanglement entropy is difficult to measure experimentally. Here, we present a novel correlation metric, capable of distinguishing MBL from AL in high-temperature spin systems. We demonstrate the use of this metric to detect localization in a natural solid-state spin system using nuclear magnetic resonance (NMR). We engineer the natural Hamiltonian to controllably introduce disorder and interactions, and observe the emergence of localization. In particular, while our correlation metric saturates for AL, it slowly keeps increasing for MBL, demonstrating analogous features to entanglement entropy, as we show in simulations. Our results show that our NMR techniques, akin to measuring out-of-time correlations, are well suited for studying localization in spin systems.

Spatially resolved nuclear spin relaxation, electron spin relaxation and light absorption in swift heavy ion irradiated LiF crystals.

PubMed

Stork, H; Dinse, K-P; Ditter, M; Fujara, F; Masierak, W; Neumann, R; Schuster, B; Schwartz, K; Trautmann, C

2010-05-12

Spatially resolved (19)F and (7)Li spin-lattice relaxation rates are measured for LiF single crystals after irradiation with two kinds of swift heavy ions ((12)C of 133 MeV and (208)Pb of 1.78 GeV incident energy). Like in earlier studies on (130)Xe and (238)U irradiated LiF crystals, we found a strong enhancement of the nuclear spin-lattice relaxation rate within the ion penetration depth and a slight--but still significant--enhancement beyond. By evaluating the nuclear relaxation rate enhancement within the ion range after irradiation with different projectiles, a universal relationship between the spin-lattice relaxation rate and the dose is deduced. The results of accompanying X-band electron paramagnetic resonance relaxation measurements and optical absorption spectroscopy are included in a physical interpretation of this relationship. Also the reason for the enhanced relaxation rate beyond the ion range is further discussed.

Zeeman perturbed nuclear quadrupole spin echo envelope modulations for spin 3/2 nuclei in polycrystalline specimens

NASA Astrophysics Data System (ADS)

Ramachandran, R.; Narasimhan, P. T.

The results of theoretical and experimental studies of Zeeman-perturbed nuclear quadrupole spin echo envelope modulations (ZSEEM) for spin 3/2 nuclei in polycrystalline specimens are presented. The response of the Zeeman-perturbed spin ensemble to resonant two pulse excitations has been calculated using the density matrix formalism. The theoretical calculation assumes a parallel orientation of the external r.f. and static Zeeman fields and an arbitrary orientation of these fields to the principal axes system of the electric field gradient. A numerical powder averaging procedure has been adopted to simulate the response of the polycrystalline specimens. Using a coherent pulsed nuclear quadrupole resonance spectrometer the ZSEEM patterns of the 35Cl nuclei have been recorded in polycrystalline specimens of potassium chlorate, barium chlorate, mercuric chloride (two sites) and antimony trichloride (two sites) using the π/2-τ-π/2 sequence. The theoretical and experimental ZSEEM patterns have been compared. In the case of mercuric chloride, the experimental 35Cl ZSEEM patterns are found to be nearly identical for the two sites and correspond to a near-zero value of the asymmetry parameter, η, of the electric field gradient tensor. The difference in the η values for the two 35Cl sites (η ˜0·06 and η˜0·16) in antimony trichloride is clearly reflected in the experimental and theoretical ZSEEM patterns. The present study indicates the feasibility of evaluating η for spin 3/2 nuclei in polycrystalline specimens from ZSEEM investigations.

Efficient Organometallic Spin Filter between Single-Wall Carbon Nanotube or Graphene Electrodes

NASA Astrophysics Data System (ADS)

Koleini, Mohammad; Paulsson, Magnus; Brandbyge, Mads

2007-05-01

We present a theoretical study of spin transport in a class of molecular systems consisting of an organometallic benzene-vanadium cluster placed in between graphene or single-wall carbon-nanotube-model contacts. Ab initio modeling is performed by combining spin density functional theory and nonequilibrium Green’s function techniques. We consider weak and strong cluster-contact bonds. Depending on the bonding we find from 73% (strong bonds) up to 99% (weak bonds) spin polarization of the electron transmission, and enhanced polarization with increased cluster length.

Electron and nuclear spin interactions in the optical spectra of single GaAs quantum dots.

PubMed

Gammon, D; Efros, A L; Kennedy, T A; Rosen, M; Katzer, D S; Park, D; Brown, S W; Korenev, V L; Merkulov, I A

2001-05-28

Fine and hyperfine splittings arising from electron, hole, and nuclear spin interactions in the magneto-optical spectra of individual localized excitons are studied. We explain the magnetic field dependence of the energy splitting through competition between Zeeman, exchange, and hyperfine interactions. An unexpectedly small hyperfine contribution to the splitting close to zero applied field is described well by the interplay between fluctuations of the hyperfine field experienced by the nuclear spin and nuclear dipole/dipole interactions.

Investigation of the spin Seebeck effect and anomalous Nernst effect in a bulk carbon material

NASA Astrophysics Data System (ADS)

Wongjom, Poramed; Pinitsoontorn, Supree

2018-03-01

Since the discovery of the spin Seebeck effect (SSE) in 2008, it has become one of the most active topics in the spin caloritronics research field. It opened up a new way to create the spin current by a combination of magnetic fields and heat. The SSE was observed in many kinds of materials including metallic, semiconductor, or insulating magnets, as well as non-magnetic materials. On the other hand, carbon-based materials have become one of the most exciting research areas recently due to its low cost, abundance and some exceptional functionalities. In this work, we have investigated the possibility of the SSE in bulk carbon materials for the first time. Thin platinum film (Pt), coated on the smoothened surface of the bulk carbon, was used as the spin detector via the inverse spin Hall effect (ISHE). The experiment for observing longitudinal SSE in the bulk carbon was set up by applying a magnetic field up to 30 kOe to the sample with the direction perpendicular to the applied temperature gradient. The induced voltage from the SSE was extracted. However, for conductive materials, e.g. carbon, the voltage signal under this set up could be a combination of the SSE and the anomalous Nernst effect (ANE). Therefore, two measurement configurations were carried out, i.e. the in-plane magnetization (IM), and the perpendicular-to-plane magnetization (PM). For the IM configuration, the SSE + ANE signals were detected where as the only ANE signal existed in the PM configuration. The results showed that there were the differences between the voltage signals from the IM and PM configurations implying the possibility of the SSE in the bulk carbon material. Moreover, it was found that the difference in the IM and PM signals was a function of the magnetic field strength, temperature difference, and measurement temperature. Although the magnitude of the possible SSE voltage in this experiment was rather low (less than 0.5 μV at 50 K), this research showed that potential of using

Interaction of Strain and Nuclear Spins in Silicon: Quadrupolar Effects on Ionized Donors

NASA Astrophysics Data System (ADS)

Franke, David P.; Hrubesch, Florian M.; Künzl, Markus; Becker, Hans-Werner; Itoh, Kohei M.; Stutzmann, Martin; Hoehne, Felix; Dreher, Lukas; Brandt, Martin S.

2015-07-01

The nuclear spins of ionized donors in silicon have become an interesting quantum resource due to their very long coherence times. Their perfect isolation, however, comes at a price, since the absence of the donor electron makes the nuclear spin difficult to control. We demonstrate that the quadrupolar interaction allows us to effectively tune the nuclear magnetic resonance of ionized arsenic donors in silicon via strain and determine the two nonzero elements of the S tensor linking strain and electric field gradients in this material to S11=1.5 ×1022 V /m2 and S44=6 ×1022 V /m2 . We find a stronger benefit of dynamical decoupling on the coherence properties of transitions subject to first-order quadrupole shifts than on those subject to only second-order shifts and discuss applications of quadrupole physics including mechanical driving of magnetic resonance, cooling of mechanical resonators, and strain-mediated spin coupling.

Ground-state cooling of a carbon nanomechanical resonator by spin-polarized current.

PubMed

Stadler, P; Belzig, W; Rastelli, G

2014-07-25

We study the nonequilibrium steady state of a mechanical resonator in the quantum regime realized by a suspended carbon nanotube quantum dot in contact with two ferromagnets. Because of the spin-orbit interaction and/or an external magnetic field gradient, the spin on the dot couples directly to the flexural eigenmodes. Accordingly, the nanomechanical motion induces inelastic spin flips of the tunneling electrons. A spin-polarized current at finite bias voltage causes either heating or active cooling of the mechanical modes. We show that maximal cooling is achieved at resonant transport when the energy splitting between two dot levels of opposite spin equals the vibrational frequency. Even for weak electron-resonator coupling and moderate polarizations we can achieve ground-state cooling with a temperature of the leads, for instance, of T = 10 ω.

Development of qualitative and quantitative analysis methods in pharmaceutical application with new selective signal excitation methods for 13 C solid-state nuclear magnetic resonance using 1 H T1rho relaxation time.

PubMed

Nasu, Mamiko; Nemoto, Takayuki; Mimura, Hisashi; Sako, Kazuhiro

2013-01-01

Most pharmaceutical drug substances and excipients in formulations exist in a crystalline or amorphous form, and an understanding of their state during manufacture and storage is critically important, particularly in formulated products. Carbon 13 solid-state nuclear magnetic resonance (NMR) spectroscopy is useful for studying the chemical and physical state of pharmaceutical solids in a formulated product. We developed two new selective signal excitation methods in (13) C solid-state NMR to extract the spectrum of a target component from such a mixture. These methods were based on equalization of the proton relaxation time in a single domain via rapid intraproton spin diffusion and the difference in proton spin-lattice relaxation time in the rotating frame ((1) H T1rho) of individual components in the mixture. Introduction of simple pulse sequences to one-dimensional experiments reduced data acquisition time and increased flexibility. We then demonstrated these methods in a commercially available drug and in a mixture of two saccharides, in which the (13) C signals of the target components were selectively excited, and showed them to be applicable to the quantitative analysis of individual components in solid mixtures, such as formulated products, polymorphic mixtures, or mixtures of crystalline and amorphous phases. Copyright © 2012 Wiley Periodicals, Inc.

High temperature spin dynamics in linear magnetic chains, molecular rings, and segments by nuclear magnetic resonance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adelnia, Fatemeh; Lascialfari, Alessandro; Dipartimento di Fisica, Università degli Studi di Pavia and INSTM, Pavia

2015-05-07

We present the room temperature proton nuclear magnetic resonance (NMR) nuclear spin-lattice relaxation rate (NSLR) results in two 1D spin chains: the Heisenberg antiferromagnetic (AFM) Eu(hfac){sub 3}NITEt and the magnetically frustrated Gd(hfac){sub 3}NITEt. The NSLR as a function of external magnetic field can be interpreted very well in terms of high temperature spin dynamics dominated by a long time persistence of the decay of the two-spin correlation function due to the conservation of the total spin value for isotropic Heisenberg chains. The high temperature spin dynamics are also investigated in Heisenberg AFM molecular rings. In both Cr{sub 8} closed ringmore » and in Cr{sub 7}Cd and Cr{sub 8}Zn open rings, i.e., model systems for a finite spin segment, an enhancement of the low frequency spectral density is found consistent with spin diffusion but the high cut-off frequency due to intermolecular anisotropic interactions prevents a detailed analysis of the spin diffusion regime.« less

Probing Nuclear Spin Effects on Electronic Spin Coherence via EPR Measurements of Vanadium(IV) Complexes.

PubMed

Graham, Michael J; Krzyaniak, Matthew D; Wasielewski, Michael R; Freedman, Danna E

2017-07-17

Quantum information processing (QIP) has the potential to transform numerous fields from cryptography, to finance, to the simulation of quantum systems. A promising implementation of QIP employs unpaired electronic spins as qubits, the fundamental units of information. Though molecular electronic spins offer many advantages, including chemical tunability and facile addressability, the development of design principles for the synthesis of complexes that exhibit long qubit superposition lifetimes (also known as coherence times, or T 2 ) remains a challenge. As nuclear spins in the local qubit environment are a primary cause of shortened superposition lifetimes, we recently conducted a study which employed a modular spin-free ligand scaffold to place a spin-laden propyl moiety at a series of fixed distances from an S = 1 / 2 vanadium(IV) ion in a series of vanadyl complexes. We found that, within a radius of 4.0(4)-6.6(6) Å from the metal center, nuclei did not contribute to decoherence. To assess the generality of this important design principle and test its efficacy in a different coordination geometry, we synthesized and investigated three vanadium tris(dithiolene) complexes with the same ligand set employed in our previous study: K 2 [V(C 5 H 6 S 4 ) 3 ] (1), K 2 [V(C 7 H 6 S 6 ) 3 ] (2), and K 2 [V(C 9 H 6 S 8 ) 3 ] (3). We specifically interrogated solutions of these complexes in DMF-d 7 /toluene-d 8 with pulsed electron paramagnetic resonance spectroscopy and electron nuclear double resonance spectroscopy and found that the distance dependence present in the previously synthesized vanadyl complexes holds true in this series. We further examined the coherence properties of the series in a different solvent, MeCN-d 3 /toluene-d 8 , and found that an additional property, the charge density of the complex, also affects decoherence across the series. These results highlight a previously unknown design principle for augmenting T 2 and open new pathways for the

Curvature-enhanced Spin-orbit Coupling and Spinterface Effect in Fullerene-based Spin Valves

NASA Astrophysics Data System (ADS)

Liang, Shiheng; Geng, Rugang; Yang, Baishun; Zhao, Wenbo; Chandra Subedi, Ram; Li, Xiaoguang; Han, Xiufeng; Nguyen, Tho Duc

2016-01-01

We investigated curvature-enhanced spin-orbit coupling (SOC) and spinterface effect in carbon-based organic spin valves (OSVs) using buckyball C60 and C70 molecules. Since the naturally abundant 12C has spinless nuclear, the materials have negligible hyperfine interaction (HFI) and the same intrinsic SOC, but different curvature SOC due to their distinct curvatures. We fitted the thickness dependence of magnetoresistance (MR) in OSVs at various temperatures using the modified Jullière equation. We found that the spin diffusion length in the C70 film is above 120 nm, clearly longer than that in C60 film at all temperatures. The effective SOC ratio of the C70 film to the C60 film was estimated to be about 0.8. This was confirmed by the magneto-electroluminescence (MEL) measurement in fullerene-based light emitting diodes (LED). Next, the effective spin polarization in C70-based OSVs is smaller than that in C60-based OSVs implying that they have different spinterface effect. First principle calculation study shows that the spin polarization of the dz2 orbital electrons of Co atoms contacted with C60 is larger causing better effective spin polarization at the interface.

The nuclear spin response to intermediate energy protons

NASA Astrophysics Data System (ADS)

Baker, F. T.; Bimbot, L.; Castel, B.; Fergerson, R. W.; Glashausser, C.; Green, A.; Hausser, O.; Hicks, K.; Jones, K.; Miller, C. A.; Nanda, S. K.; Smith, R. D.; Vetterli, M.; Wambach, J.; Abegg, R.; Beatty, D.; Cupps, V.; Djalali, C.; Henderson, R.; Jackson, K. P.; Jeppeson, R.; Lisantti, J.; Morlet, M.; Sawafta, R.; Unkelbach, W.; Willis, A.; Yen, S.

1990-03-01

Measurements of the spin-flip probability Snn for inclusive inelastic proton scattering around 300 MeV from nuclei between 12C and 90Zr show that an enhanced spin response near 40 MeV excitation at q ∼ 100 MeV/ c is a general feature of nuclear structure. Data for 40Ca at 800 MeV confirm that the enhancement is not a peculiarity of 300 MeV scattering. In addition, measurements in 44Ca up to 75 MeV show that the enhancement cannot be attributed solely to a relatively narrow resonance. Continuum RPA calculations suggest that the enhancement is due to the exhaustion of most S = 0 strength at lower energy and a shift of S = 1 strength to higher energy.

Investigation of a new model of dipolar-coupled nuclear spin relaxation and applications of dynamic nuclear polarization

NASA Astrophysics Data System (ADS)

Sorte, Eric G.

This work presents the results of various investigations using various techniques of hyperpolarizing the nuclei of atoms. Hyperpolarization implies magnetic order in excess of the thermal order obtained naturally as described by Curie's law. The main portion of this work presents the results of a detailed experimental exploration of predictions arising from a new model of transverse nuclear spin relaxation in quantum systems, based on possible manifestations of microscopic chaos in quantum systems. Experiments have been carried out on a number of hyperpolarized xenon samples, each differing in its relative percentage of xenon isotopes in order to vary the homonuclear and heteronuclear dipole couplings in the spin system. The experiments were performed under a variety of conditions in an attempt to observe the behaviors predicted by the model. Additionally, much more extensive measurements were made on a number of samples of solid CaF2 in both single crystal and powder forms. These samples, although thermally polarized, were observed with superior signal to noise ratios than even the hyperpolarized xenon solids, allowing for more precise measurements for comparison to the theory. This work thus contains the first experimental evidence for the majority of the model's predictions. Additionally, this work contains the first precise measurements of the frequency-shift enhancement parameters for 129Xe and krypton in the presence of spin-polarized Rb. The determination of these important numbers will be useful to many groups who utilize spin-exchange optical pumping in their labs. This work built on the prior knowledge of a precise number for the frequency-shift enhancement parameter of 3He in Rb vapor. Finally, I detail work using NMR to detect nuclear-spin polarization enhancement in silicon phosphorus by a novel, photo-induced hyperpolarization technique developed by the Boehme research group at the University of Utah. Significant nuclear polarization enhancements were

Hyperpolarized 13C metabolic imaging using dissolution dynamic nuclear polarization.

PubMed

Hurd, Ralph E; Yen, Yi-Fen; Chen, Albert; Ardenkjaer-Larsen, Jan Henrik

2012-12-01

This article describes the basic physics of dissolution dynamic nuclear polarization (dissolution-DNP), and the impact of the resulting highly nonequilibrium spin states, on the physics of magnetic resonance imaging (MRI) detection. The hardware requirements for clinical translation of this technology are also presented. For studies that allow the use of externally administered agents, hyperpolarization offers a way to overcome normal magnetic resonance sensitivity limitations, at least for a brief T(1)-dependent observation window. A 10,000-100,000-fold signal-to-noise advantage provides an avenue for real-time measurement of perfusion, metabolite transport, exchange, and metabolism. The principles behind these measurements, as well as the choice of agent, and progress toward the application of hyperpolarized (13)C metabolic imaging in oncology, cardiology, and neurology are reviewed. Copyright © 2012 Wiley Periodicals, Inc.

The Key Role of Nuclear-Spin Astrochemistry

NASA Astrophysics Data System (ADS)

Le Gal, Romane; Herbst, Eric; Xie, Changjian; Guo, Hua; Talbi, Dahbia; Muller, Sebastien; Persson, Carina

2017-06-01

Thanks to the new spectroscopic windows opened by the recent generation of telescopes, a large number of molecular lines have been detected. In particular, nuclear-spin astrochemistry has gained interest owing to numerous ortho-to-para ratio (OPR) measurements for species including H_3^+, CH_2, C_3H_2, H_2O, NH_3, NH_2, H_2S, H_2CS, H_2O^+ and H_2Cl^+. Any multi-hydrogenated species can indeed present different spin configurations, if some of their hydrogen nuclei are identical, and the species thus exist in distinguishable forms, such as ortho and para. In thermal equilibrium, OPRs are only functions of the temperature and since spontaneous conversion between ortho and para states is extremely slow in comparison with typical molecular cloud lifetimes, OPRs were commonly believed to reflect a ``formation temperature''. However, observed OPRs are not always consistent with their thermal equilibrium values, as for the NH_3 and NH_2 cases. It is thus crucial to understand how interstellar OPRs are formed to constrain the information such new probes can provide. This involves a comprehensive analysis of the processes governing the interstellar nuclear-spin chemistry, including the formation and possible conversions of the different spin symmetries both in the gas and solid phases. If well understood, OPRs might afford new powerful astrophysical diagnostics on the chemical and physical conditions of their environments, and in particular could trace their thermal history. In this context, observations of non-thermal values for the OPR of the radical NH_2 toward four high-mass star-forming regions, and a 3:1 value measured for the H_2Cl^+ OPR toward diffuse and denser gas, led us to develop detailed studies of the mechanisms involved in obtaining such OPRs with the aid of quasi-classical trajectory calculations. We will present these new promising results, improving our understanding of the interstellar medium. Persson et al. 2016, A&A, 586, A128, Neufeld et al. 2016, Ap

Quantum Control and Entanglement of Spins in Silicon Carbide

NASA Astrophysics Data System (ADS)

Klimov, Paul

Over the past several decades silicon carbide (SiC) has matured into a versatile material platform for high-power electronics and optoelectronic and micromechanical devices. Recent advances have also established SiC as a promising host for quantum technologies based on the spin of intrinsic defects, with the potential of leveraging existing device fabrication protocols alongside solid-state quantum control. Among these defects are the divacancies and related color centers, which have ground-state electron-spin triplets with coherence times as long as one millisecond and built-in optical interfaces operating near the telecommunication wavelengths. This rapidly developing field has prompted research into the SiC material host to understand how defect-bound electron spins interact with their surrounding nuclear spin bath. Although nuclear spins are a major source of decoherence in color-center spin systems, they are also a valuable resource since they can have coherence times that are orders of magnitude longer than electron spins. In this talk I will discuss our recent efforts to interface defect-bound electron spins in SiC with the nuclear spins of naturally occurring 29Si and 13C isotopic defects. I will discuss how the hyperfine interaction can be used to strongly initialize them, to coherently control them, to read them out, and to produce genuine electron-nuclear ensemble entanglement, all at ambient conditions. These demonstrations motivate further research into spins in SiC for prospective quantum technologies. In collaboration with A. Falk, D. Christle, K. Miao, H. Seo, V. Ivady, A. Gali, G. Galli, and D. D. Awschalom. This research was supported by the AFOSR, the NSF DMR-1306300, and the NSF Materials Research Science and Engineering Center.

All-optical control of long-lived nuclear spins in rare-earth doped nanoparticles.

PubMed

Serrano, D; Karlsson, J; Fossati, A; Ferrier, A; Goldner, P

2018-05-29

Nanoscale systems that coherently couple to light and possess spins offer key capabilities for quantum technologies. However, an outstanding challenge is to preserve properties, and especially optical and spin coherence lifetimes, at the nanoscale. Here, we report optically controlled nuclear spins with long coherence lifetimes (T 2 ) in rare-earth-doped nanoparticles. We detect spins echoes and measure a spin coherence lifetime of 2.9 ± 0.3 ms at 5 K under an external magnetic field of 9 mT, a T 2 value comparable to those obtained in bulk rare-earth crystals. Moreover, we achieve spin T 2 extension using all-optical spin dynamical decoupling and observe high fidelity between excitation and echo phases. Rare-earth-doped nanoparticles are thus the only nano-material in which optically controlled spins with millisecond coherence lifetimes have been reported. These results open the way to providing quantum light-atom-spin interfaces with long storage time within hybrid architectures.

Spectrum of the Nuclear Environment for GaAs Spin Qubits.

PubMed

Malinowski, Filip K; Martins, Frederico; Cywiński, Łukasz; Rudner, Mark S; Nissen, Peter D; Fallahi, Saeed; Gardner, Geoffrey C; Manfra, Michael J; Marcus, Charles M; Kuemmeth, Ferdinand

2017-04-28

Using a singlet-triplet spin qubit as a sensitive spectrometer of the GaAs nuclear spin bath, we demonstrate that the spectrum of Overhauser noise agrees with a classical spin diffusion model over 6 orders of magnitude in frequency, from 1 mHz to 1 kHz, is flat below 10 mHz, and falls as 1/f^{2} for frequency f≳1  Hz. Increasing the applied magnetic field from 0.1 to 0.75 T suppresses electron-mediated spin diffusion, which decreases the spectral content in the 1/f^{2} region and lowers the saturation frequency, each by an order of magnitude, consistent with a numerical model. Spectral content at megahertz frequencies is accessed using dynamical decoupling, which shows a crossover from the few-pulse regime (≲16π pulses), where transverse Overhauser fluctuations dominate dephasing, to the many-pulse regime (≳32 π pulses), where longitudinal Overhauser fluctuations with a 1/f spectrum dominate.

Nuclear spin-spin coupling in a van der Waals-bonded system: xenon dimer.

PubMed

Vaara, Juha; Hanni, Matti; Jokisaari, Jukka

2013-03-14

Nuclear spin-spin coupling over van der Waals bond has recently been observed via the frequency shift of solute protons in a solution containing optically hyperpolarized (129)Xe nuclei. We carry out a first-principles computational study of the prototypic van der Waals-bonded xenon dimer, where the spin-spin coupling between two magnetically non-equivalent isotopes, J((129)Xe - (131)Xe), is observable. We use relativistic theory at the four-component Dirac-Hartree-Fock and Dirac-density-functional theory levels using novel completeness-optimized Gaussian basis sets and choosing the functional based on a comparison with correlated ab initio methods at the nonrelativistic level. J-coupling curves are provided at different levels of theory as functions of the internuclear distance in the xenon dimer, demonstrating cross-coupling effects between relativity and electron correlation for this property. Calculations on small Xe clusters are used to estimate the importance of many-atom effects on J((129)Xe - (131)Xe). Possibilities of observing J((129)Xe - (131)Xe) in liquid xenon are critically examined, based on molecular dynamics simulation. A simplistic spherical model is set up for the xenon dimer confined in a cavity, such as in microporous materials. It is shown that the on the average shorter internuclear distance enforced by the confinement increases the magnitude of the coupling as compared to the bulk liquid case, rendering J((129)Xe - (131)Xe) in a cavity a feasible target for experimental investigation.

Multiple-Quantum Transitions and Charge-Induced Decoherence of Donor Nuclear Spins in Silicon

NASA Astrophysics Data System (ADS)

Franke, David P.; Pflüger, Moritz P. D.; Itoh, Kohei M.; Brandt, Martin S.

2017-06-01

We study single- and multiquantum transitions of the nuclear spins of an ensemble of ionized arsenic donors in silicon and find quadrupolar effects on the coherence times, which we link to fluctuating electrical field gradients present after the application of light and bias voltage pulses. To determine the coherence times of superpositions of all orders in the 4-dimensional Hilbert space, we use a phase-cycling technique and find that, when electrical effects were allowed to decay, these times scale as expected for a fieldlike decoherence mechanism such as the interaction with surrounding Si 29 nuclear spins.

Modelling the molecular composition and nuclear-spin chemistry of collapsing prestellar sources

NASA Astrophysics Data System (ADS)

Hily-Blant, P.; Faure, A.; Rist, C.; Pineau des Forêts, G.; Flower, D. R.

2018-04-01

We study the gravitational collapse of prestellar sources and the associated evolution of their chemical composition. We use the University of Grenoble Alpes Astrochemical Network (UGAN), which includes reactions involving the different nuclear-spin states of H2, H+3, and of the hydrides of carbon, nitrogen, oxygen, and sulfur, for reactions involving up to seven protons. In addition, species-to-species rate coefficients are provided for the ortho/para interconversion of the H_3^+ + H2 system and isotopic variants. The composition of the medium is followed from an initial steady state through the early phase of isothermal gravitational collapse. Both the freeze-out of the molecules on to grains and the coagulation of the grains were incorporated in the model. The predicted abundances and column densities of the spin isomers of ammonia and its deuterated forms are compared with those measured recently towards the prestellar cores H-MM1, L16293E, and Barnard B1. We find that gas-phase processes alone account satisfactorily for the observations, without recourse to grain-surface reactions. In particular, our model reproduces both the isotopologue abundance ratios and the ortho:para ratios of NH2D and NHD2 within observational uncertainties. More accurate observations are necessary to distinguish between full scrambling processes—as assumed in our gas-phase network—and direct nucleus- or atom-exchange reactions.

Modelling the molecular composition and nuclear-spin chemistryof collapsing pre-stellar sources

NASA Astrophysics Data System (ADS)

Hily-Blant, P.; Faure, A.; Rist, C.; Pineau des Forêts, G.; Flower, D. R.

2018-07-01

We study the gravitational collapse of pre-stellar sources and the associated evolution of their chemical composition. We use the University of Grenoble Alpes Astrochemical Network (UGAN), which includes reactions involving the different nuclear-spin states of H2, H_3^+, and of the hydrides of carbon, nitrogen, oxygen, and sulphur, for reactions involving up to seven protons. In addition, species-to-species rate coefficients are provided for the ortho/para interconversion of the H_3^+ + H2 system and isotopic variants. The composition of the medium is followed from an initial steady state through the early phase of isothermal gravitational collapse. Both the freeze-out of the molecules on to grains and the coagulation of the grains were incorporated in the model. The predicted abundances and column densities of the spin isomers of ammonia and its deuterated forms are compared with those measured recently towards the pre-stellar cores H-MM1, L16293E, and Barnard B1. We find that gas-phase processes alone account satisfactorily for the observations, without recourse to grain-surface reactions. In particular, our model reproduces both the isotopologue abundance ratios and the ortho:para ratios of NH2D and NHD2 within observational uncertainties. More accurate observations are necessary to distinguish between full scrambling processes - as assumed in our gas-phase network - and direct nucleus- or atom-exchange reactions.

Synthesis and characterization of carbon coated LiCo1/3Ni1/3Mn1/3O2 and bio-mass derived graphene like porous carbon electrodes for aqueous Li-ion hybrid supercapacitor

NASA Astrophysics Data System (ADS)

Ramkumar, B.; Yuvaraj, S.; Surendran, S.; Pandi, K.; Ramasamy, Hari Vignesh; Lee, Y. S.; Kalai Selvan, R.

2018-01-01

For the fabrication of aqueous Li-ion hybrid supercapacitor, carbon coated LiCo1/3Ni1/3Mn1/3O2 (or LiCo1/3Ni1/3Mn1/3O2@C composite) is synthesized by polymeric precursor method with subsequent thermal decomposition procedures for carbon coating. Graphene like porous carbon is obtained by chemical activation from the biomass of Agave Americana. The XRD analysis reveals that LiCo1/3Ni1/3Mn1/3O2 is having a hexagonal layered structure and activated carbon exists in both amorphous and graphitic nature. The TEM image infers that LiCo1/3Ni1/3Mn1/3O2 particles having the non-uniform shape with sub-micron size and the LiCo1/3Ni1/3Mn1/3O2 particles are embedded into amorphous carbon cloud in the composite. The activated carbon shows the specific surface area of 1219 m2 g-1. Finally, the fabricated aqueous LiCo1/3Ni1/3Mn1/3O2@C‖AC hybrid supercapacitor delivers the specific capacitance of 56 F g-1 with good capacity retention even after 5000 cycles.

Prediction of Nuclear Masses as a function of P and F-spin

NASA Astrophysics Data System (ADS)

Teymurazyan, Artur; Aprahamian, Ani; Georgieva, Ana

2001-10-01

Nuclear masses are one of the most important components in nucleosynthesis calculations of elemental abundances for specific stellar scenarios. Proton rich nuclei in the A=80 region are thought to be produced in the rp-process (rapid p and α-capture)involving a large number of unknown nuclei. Schatz et al.(H. Schatz et al., Phys. Rep. 294,167 (1998)) have carried out an extensive comparison of the effects on abundances that result from the use of different mass models. One of these models was a semi-empirical mass model(A. Aprahamian et al., Rev. Mex. Fis. 42, 1 (1996)) based on the relationship of the nuclear structure component of the nuclear mass on the parameter P=N_pN_n/(N_p+N_n) where N-p and Nn are the number of valence protons and neutrons. Davis et al.(E.D. Davis et al., Phys. Rev. C 44, 1655 (1991)) had used another approach involving F-spin (an approximate symmetry under particle-hole Conjugation) to predict binding energies for r-process nuclei in the Z=50-82 and N=82-126 region. In this paper, we combine structure systematics using F-spin(A. Georgieva et al., Int. J. Theor. Phys. 28, 769 (1989)) to show a simple relationship between P and F-spin for this very interesting region and to apply it to the prediction of nuclear masses in the A=80 region of nuclei.

Spin-reorientation transitions in the Cairo pentagonal magnet Bi 4 Fe 5 O 13 F

DOE PAGES

Tsirlin, Alexander A.; Rousochatzakis, Ioannis; Filimonov, Dmitry; ...

2017-09-19

Here, we show that interlayer spins play a dual role in the Cairo pentagonal magnet Bi 4Fe 5O 13F, on one hand mediating the three-dimensional magnetic order, and on the other driving spin-reorientation transitions both within and between the planes. The corresponding sequence of magnetic orders unraveled by neutron diffraction and Mössbauer spectroscopy features two orthogonal magnetic structures described by opposite local vector chiralities, and an intermediate, partly disordered phase with nearly collinear spins. A similar collinear phase has been predicted theoretically to be stabilized by quantum fluctuations, but Bi 4Fe 5O 13F is very far from the relevant parametermore » regime. While the observed in-plane reorientation cannot be explained by any standard frustration mechanism, our ab initio band-structure calculations reveal strong single-ion anisotropy of the interlayer Fe 3+ spins that turns out to be instrumental in controlling the local vector chirality and the associated interlayer order.« less

Spin-reorientation transitions in the Cairo pentagonal magnet Bi4Fe5O13F

NASA Astrophysics Data System (ADS)

Tsirlin, Alexander A.; Rousochatzakis, Ioannis; Filimonov, Dmitry; Batuk, Dmitry; Frontzek, Matthias; Abakumov, Artem M.

2017-09-01

We show that interlayer spins play a dual role in the Cairo pentagonal magnet Bi4Fe5O13F , on one hand mediating the three-dimensional magnetic order, and on the other driving spin-reorientation transitions both within and between the planes. The corresponding sequence of magnetic orders unraveled by neutron diffraction and Mössbauer spectroscopy features two orthogonal magnetic structures described by opposite local vector chiralities, and an intermediate, partly disordered phase with nearly collinear spins. A similar collinear phase has been predicted theoretically to be stabilized by quantum fluctuations, but Bi4Fe5O13F is very far from the relevant parameter regime. While the observed in-plane reorientation cannot be explained by any standard frustration mechanism, our ab initio band-structure calculations reveal strong single-ion anisotropy of the interlayer Fe3 + spins that turns out to be instrumental in controlling the local vector chirality and the associated interlayer order.

Implanted bismuth donors in 28-Si: Process development and electron spin resonance measurements

NASA Astrophysics Data System (ADS)

Weis, C. D.; Lo, C. C.; Lang, V.; George, R. E.; Tyryshkin, A. M.; Bokor, J.; Lyon, S. A.; Morton, J. J. L.; Schenkel, T.

2012-02-01

Spins of donor atoms in silicon are excellent qubit candidates. Isotope engineered substrates provide a nuclear spin free host environment, resulting in long spin coherence times [1,2]. The capability of swapping quantum information between electron and nuclear spins can enable quantum communication and gate operation via the electron spin and quantum memory via the nuclear spin [2]. Spin properties of donor qubit candidates in silicon have been studied mostly for phosphorous and antimony [1-3]. Bismuth donors in silicon exhibit a zero field splitting of 7.4 GHz and have attracted attention as potential nuclear spin memory and spin qubit candidates [4,5] that could be coupled to superconducting resonators [4,6]. We report on progress in the formation of bismuth doped 28-Si epi layers by ion implantation, electrical dopant activation and their study via pulsed electron spin resonance measurements showing narrow linewidths and good coherence times. [4pt] [1] A. M. Tyryshkin, et al. arXiv: 1105.3772 [2] J. J. L. Morton, et al. Nature (2008) [3] T. Schenkel, et al APL 2006; F. R. Bradbury, et al. PRL (2006) [4] R. E. George, et al. PRL (2010) [5] G. W. Morley, et al. Nat Mat (2010) [6] M. Hatridge, et al. PRB (2011), R. Vijay, et al. APL (2010) This work was supported by NSA (100000080295) and DOE (DE-AC02-05CH11231).

Pyrolytic carbon-coated nuclear fuel

DOEpatents

Lindemer, Terrence B.; Long, Jr., Ernest L.; Beatty, Ronald L.

1978-01-01

An improved nuclear fuel kernel having at least one pyrolytic carbon coating and a silicon carbon layer is provided in which extensive interaction of fission product lanthanides with the silicon carbon layer is avoided by providing sufficient UO.sub.2 to maintain the lanthanides as oxides during in-reactor use of said fuel.

Observation of zero-point quantum fluctuations of a single-molecule magnet through the relaxation of its nuclear spin bath.

PubMed

Morello, A; Millán, A; de Jongh, L J

2014-03-21

A single-molecule magnet placed in a magnetic field perpendicular to its anisotropy axis can be truncated to an effective two-level system, with easily tunable energy splitting. The quantum coherence of the molecular spin is largely determined by the dynamics of the surrounding nuclear spin bath. Here we report the measurement of the nuclear spin-lattice relaxation rate 1/T1n in a single crystal of the single-molecule magnet Mn12-ac, at T ≈ 30 mK in perpendicular fields B⊥ up to 9 T. The relaxation channel at B ≈ 0 is dominated by incoherent quantum tunneling of the Mn12-ac spin S, aided by the nuclear bath itself. However for B⊥>5 T we observe an increase of 1/T1n by several orders of magnitude up to the highest field, despite the fact that the molecular spin is in its quantum mechanical ground state. This striking observation is a consequence of the zero-point quantum fluctuations of S, which allow it to mediate the transfer of energy from the excited nuclear spin bath to the crystal lattice at much higher rates. Our experiment highlights the importance of quantum fluctuations in the interaction between an "effective two-level system" and its surrounding spin bath.

Spin-orbit coupling and the static polarizability of single-wall carbon nanotubes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diniz, Ginetom S., E-mail: ginetom@gmail.com; Ulloa, Sergio E.

2014-07-14

We calculate the static longitudinal polarizability of single-wall carbon tubes in the long wavelength limit taking into account spin-orbit effects. We use a four-orbital orthogonal tight-binding formalism to describe the electronic states and the random phase approximation to calculate the dielectric function. We study the role of both the Rashba as well as the intrinsic spin-orbit interactions on the longitudinal dielectric response, i.e., when the probing electric field is parallel to the nanotube axis. The spin-orbit interaction modifies the nanotube electronic band dispersions, which may especially result in a small gap opening in otherwise metallic tubes. The bandgap size andmore » state features, the result of competition between Rashba and intrinsic spin-orbit interactions, result in drastic changes in the longitudinal static polarizability of the system. We discuss results for different nanotube types and the dependence on nanotube radius and spin-orbit couplings.« less

Nuclear Spin Attenuates the Anesthetic Potency of Xenon Isotopes in Mice: Implications for the Mechanisms of Anesthesia and Consciousness.

PubMed

Li, Na; Lu, Dongshi; Yang, Lei; Tao, Huan; Xu, Younian; Wang, Chenchen; Fu, Lisha; Liu, Hui; Chummum, Yatisha; Zhang, Shihai

2018-04-11

Xenon is an elemental anesthetic with nine stable isotopes. Nuclear spin is a quantum property which may differ among isotopes. Xenon 131 (Xe) has nuclear spin of 3/2, xenon 129 (Xe) a nuclear spin of 1/2, and the other seven isotopes have no nuclear spin. This study was aimed to explore the effect of nuclear spin on xenon anesthetic potency. Eighty C57BL/6 male mice (7 weeks old) were randomly divided into four groups, xenon 132 (Xe), xenon 134 (Xe), Xe, and Xe groups. Due to xenon's low potency, loss of righting reflex ED50 for mice to xenon was determined with 0.50% isoflurane. Loss of righting reflex ED50 of isoflurane was also measured, and the loss of righting reflex ED50 values of the four xenon isotopes were then calculated. The exact polarizabilities of the isotopes were calculated. Combined with 0.50% isoflurane, the loss of righting reflex ED50 values were 15 ± 4%, 16 ± 5%, 22 ± 5%, and 23 ± 7% for Xe, Xe, Xe, and Xe, respectively. For xenon alone, the loss of righting reflex ED50 values of Xe, Xe, Xe, and Xe were 70 ± 4%, 72 ± 5%, 99 ± 5%, and 105 ± 7%, respectively. Four isotopes had a same exact polarizability of 3.60 Å. Xenon isotopes with nuclear spin are less potent than those without, and polarizability cannot account for the difference. The lower anesthetic potency of Xe may be the result of it participating in conscious processing and therefore partially antagonizing its own anesthetic potency. Nuclear spin is a quantum property, and our results are consistent with theories that implicate quantum mechanisms in consciousness.

Nuclear spin imaging with hyperpolarized nuclei created by brute force method

NASA Astrophysics Data System (ADS)

Tanaka, Masayoshi; Kunimatsu, Takayuki; Fujiwara, Mamoru; Kohri, Hideki; Ohta, Takeshi; Utsuro, Masahiko; Yosoi, Masaru; Ono, Satoshi; Fukuda, Kohji; Takamatsu, Kunihiko; Ueda, Kunihiro; Didelez, Jean-P.; Prossati, Giorgio; de Waard, Arlette

2011-05-01

We have been developing a polarized HD target for particle physics at the SPring-8 under the leadership of the RCNP, Osaka University for the past 5 years. Nuclear polarizaton is created by means of the brute force method which uses a high magnetic field (~17 T) and a low temperature (~ 10 mK). As one of the promising applications of the brute force method to life sciences we started a new project, "NSI" (Nuclear Spin Imaging), where hyperpolarized nuclei are used for the MRI (Magnetic Resonance Imaging). The candidate nuclei with spin ½hslash are 3He, 13C, 15N, 19F, 29Si, and 31P, which are important elements for the composition of the biomolecules. Since the NMR signals from these isotopes are enhanced by orders of magnitudes, the spacial resolution in the imaging would be much more improved compared to the practical MRI used so far. Another advantage of hyperpolarized MRI is that the MRI is basically free from the radiation, while the problems of radiation exposure caused by the X-ray CT or PET (Positron Emission Tomography) cannot be neglected. In fact, the risk of cancer for Japanese due to the radiation exposure through these diagnoses is exceptionally high among the advanced countries. As the first step of the NSI project, we are developing a system to produce hyperpolarized 3He gas for the diagnosis of serious lung diseases, for example, COPD (Chronic Obstructive Pulmonary Disease). The system employs the same 3He/4He dilution refrigerator and superconducting solenoidal coil as those used for the polarized HD target with some modification allowing the 3He Pomeranchuk cooling and the following rapid melting of the polarized solid 3He to avoid the depolarization. In this report, the present and future steps of our project will be outlined with some latest experimental results.

Transient nutation electron spin resonance spectroscopy on spin-correlated radical pairs: A theoretical analysis on hyperfine-induced nuclear modulations

NASA Astrophysics Data System (ADS)

Weber, Stefan; Kothe, Gerd; Norris, James R.

1997-04-01

The influence of anisotropic hyperfine interaction on transient nutation electron paramagnetic resonance (EPR) of light-induced spin-correlated radical pairs is studied theoretically using the density operator formalism. Analytical expressions for the time evolution of the transient EPR signal during selective microwave excitation of single transitions are derived for a model system comprised of a weakly coupled radical pair and one hyperfine-coupled nucleus with I=1/2. Zero-quantum electron coherence and single-quantum nuclear coherence are created as a result of the sudden light-induced generation of the radical pair state from a singlet-state precursor. Depending on the relative sizes of the nuclear Zeeman frequency and the secular and pseudo-secular parts of the hyperfine coupling, transitions between levels with different nuclear spin orientations are predicted to modulate the time-dependent EPR signal. These modulations are in addition to the well-known transient nutations and electron zero-quantum precessions. Our calculations provide insight into the mechanism of recent experimental observations of coherent nuclear modulations in the time-resolved EPR signals of doublets and radical pairs. Two distinct mechanisms of the modulations are presented for various microwave magnetic field strengths. The first modulation scheme arises from electron and nuclear coherences initiated by the laser excitation pulse and is "read out" by the weak microwave magnetic field. While the relative modulation depth of these oscillations with respect to the signal intensity is independent of the Rabi frequency, ω1, the frequencies of this coherence phenomenon are modulated by the effective microwave amplitude and determined by the nuclear Zeeman interaction and hyperfine coupling constants as well as the electron-electron spin exchange and dipolar interactions between the two radical pair halves. In a second mechanism the modulations are both created and detected by the microwave

Quantification of the "global" authigenic carbonate δ13C value and implications for carbon cycling

NASA Astrophysics Data System (ADS)

Loyd, S. J.

2017-12-01

Relationships among early Earth ocean chemistry, atmospheric chemistry and the evolution/radiation of life have been inferred from carbon isotope compositions (δ13C) of marine carbonates. Under steady-state conditions, the isotope compositions of marine carbonates reflect both the amount and δ13C of carbon entering and leaving the oceans. Recently the traditional "two-output" (marine carbonate and organic matter) mass-balance equation has been modified to include a third, authigenic carbonate output term. However, the formation mechanisms of authigenic carbonates remain poorly understood, particularly from a global prospective. The utility of the new mass-balance approach will be limited until authigenic carbonates are better characterized (e.g., through δ13C analyses). Authigenic carbonates form largely as a result of 1) the respiratory degradation of organic matter (e.g., sulfate reduction), 2) the oxidation of methane and 3) the production of methane. These major reaction pathways can produce authigenic carbonates with highly variable δ13C compositions (δ13Cac). Spatiotemporal variation in the extent and prevalence of different pathways therefore exert a first order control on "global" δ13Cac. Here, values are compiled from new and existing data sets and a modern, global δ13Cac is calculated. When calculated as an average of all data or an averaged mean of individual sites, this value is very similar to normal marine sedimentary organic matter. This finding suggests that marine sediments behave largely as closed systems in the context of organic matter degradation and carbonate authigenesis. In addition, the lack of significant difference between authigenic and organic δ13C implies that these two mass-balance output terms can be considered collectively in more recent time intervals. It may be appropriate to separate these two terms when characterizing more ancient settings when redox characteristics promoted more reducing organic matter degradation

Curvature-enhanced Spin-orbit Coupling and Spinterface Effect in Fullerene-based Spin Valves

PubMed Central

Liang, Shiheng; Geng, Rugang; Yang, Baishun; Zhao, Wenbo; Chandra Subedi, Ram; Li, Xiaoguang; Han, Xiufeng; Nguyen, Tho Duc

2016-01-01

We investigated curvature-enhanced spin-orbit coupling (SOC) and spinterface effect in carbon-based organic spin valves (OSVs) using buckyball C60 and C70 molecules. Since the naturally abundant 12C has spinless nuclear, the materials have negligible hyperfine interaction (HFI) and the same intrinsic SOC, but different curvature SOC due to their distinct curvatures. We fitted the thickness dependence of magnetoresistance (MR) in OSVs at various temperatures using the modified Jullière equation. We found that the spin diffusion length in the C70 film is above 120 nm, clearly longer than that in C60 film at all temperatures. The effective SOC ratio of the C70 film to the C60 film was estimated to be about 0.8. This was confirmed by the magneto-electroluminescence (MEL) measurement in fullerene-based light emitting diodes (LED). Next, the effective spin polarization in C70-based OSVs is smaller than that in C60-based OSVs implying that they have different spinterface effect. First principle calculation study shows that the spin polarization of the dz2 orbital electrons of Co atoms contacted with C60 is larger causing better effective spin polarization at the interface. PMID:26786047

Conformational study of 13C-enriched fibroin in the solid state, using the cross polarization nuclear magnetic resonance method.

PubMed

Fujiwara, T; Kobayashi, Y; Kyogoku, Y; Kataoka, K

1986-01-05

Silk fibroin with the alanyl carboxyl carbon enriched with 13C was obtained by giving a diet containing 13C-enriched alanine to the larvae of Bombyx mori and Antheraea pernyi at the fifth instar. Sericin-free fibroin fibers were prepared from cocoons, and gut was made from the liquid silk in the gland. The final 13C content was about 13%. Cross polarization/magic angle sample spinning spectra at 25 MHz and 75 MHz were measured for each sample at different orientations. Spectra were simulated using the principal values and orientations of the shielding tensor in the alanine crystal. The results indicate that the beta-structure of the fibroin may be a little more flattened than the typical pleated sheet beta-structure.

Spin polarization measurements and sensor applications in thin films and carbon nanotube-based devices

NASA Astrophysics Data System (ADS)

Sanders, Jeff T.

The unique properties of carbon nanotubes (CNTs) show a great deal of potential for nanoelectronic devices, spintronic devices, biosensing and chemical sensing applications. Their applicability as interconnects for spintronic devices derives from their one-dimensionality and theoretically predicted preservation of spin current. In this work, we combine an investigation of spin polarization in materials such as half-metallic oxides in thin film and bulk form with studies on several aspects of CNTs for sensing and spin transport applications. These two areas of study are intimately related within the umbrella of spin-electronics and nanoscale sensors that are being pursued with great topical interest in recent times. A measurement system has been developed to perform Point-Contact Andreev Reflection (PCAR) in the presence of variable magnetic fields and temperatures. It was designed and built, accepted for patent by the USF, and submitted to the U.S. Patent Office. A study of spin polarization in superconductor-magnet junctions has been performed over a wide range in magnetic fields (0 to 3T) and temperature (2 to 300K) on several systems including Cu, SrRuO3, LaSrMnO3, and CrO2. Spin transport experiments have been extended to single walled carbon nanotube (SWNT) networks in order to explore spin transport in nanotube networks for potential sensor applications. Carbon nanotube networks have been used as the electronic material for chemical and biological sensing where capacitance and conductance response to the adsorbtion of a chemical or biological analyte are simultaneously measured and a very fast response and recovery is observed. Chemical specificity has been investigated through different means since a goal of the U.S. Navy is to have an array of these sensors, each chemically specific to a unique analyte. Finally, research is ongoing in the analysis of our PCAR spectra in the SrRuO3 series and the La1-x(Ca, Ba, Sr)xMnO 3 to investigate the square root

Mechanism of nuclear spin initiated para-H2 to ortho-H2 conversion.

PubMed

Buntkowsky, G; Walaszek, B; Adamczyk, A; Xu, Y; Limbach, H-H; Chaudret, B

2006-04-28

In this paper a quantitative explanation for a diamagnetic ortho/para H2 conversion is given. The description is based on the quantum-mechanical density matrix formalism originally developed by Alexander and Binsch for studies of exchange processes in NMR spectra. Only the nuclear spin system is treated quantum-mechanically. Employing the model of a three spin system, the reactions of the hydrogen gas with the catalysts are treated as a phenomenological rate process, described by a rate constant. Numerical calculations reveal that for nearly all possible geometrical arrangements of the three spin system an efficient spin conversion is obtained. Only in the chemically improbable case of a linear group H-X-H no spin conversion is obtained. The efficiency of the spin conversion depends strongly on the lifetime of the H-X-H complex and on the presence of exchange interactions between the two hydrogens. Even moderate exchange couplings cause a quench of the spin conversion. Thus a sufficiently strong binding of the dihydrogen to the S spin is necessary to render the quenching by the exchange interaction ineffective.

INTRAMOLECULAR MOTION AND REORIENTATIONAL BARRIERS IN 9-FLUORENONE, 4-METHYL-9-FLUORENONE AND 4,5-DIMETHYL-9-FLUORENONE

EPA Science Inventory

Carbon-13 nuclear magnetic resonance spin-lattice relaxation times and nuclear Overhauser enhancements were measured as functions of temperature for the hydrogen-bearing carbons in 9-fluorenone, 4-methyl-9-fluorenone, and 4,5-dimethyl-9-fluorenone. Reorientational diffusion const...

Effect of deformation and orientation on spin orbit density dependent nuclear potential

NASA Astrophysics Data System (ADS)

Mittal, Rajni; Kumar, Raj; Sharma, Manoj K.

2017-11-01

Role of deformation and orientation is investigated on spin-orbit density dependent part VJ of nuclear potential (VN=VP+VJ) obtained within semi-classical Thomas Fermi approach of Skyrme energy density formalism. Calculations are performed for 24-54Si+30Si reactions, with spherical target 30Si and projectiles 24-54Si having prolate and oblate shapes. The quadrupole deformation β2 is varying within range of 0.023 ≤ β2 ≤0.531 for prolate and -0.242 ≤ β2 ≤ -0.592 for oblate projectiles. The spin-orbit dependent potential gets influenced significantly with inclusion of deformation and orientation effect. The spin-orbit barrier and position gets significantly influenced by both the sign and magnitude of β2-deformation. Si-nuclei with β22<0 have higher spin-orbit barrier (compact spin-orbit configuration) in comparison to systems with β2>0. The possible role of spin-orbit potential on barrier characteristics such as barrier height, barrier curvature and on the fusion pocket is also probed. In reference to prolate and oblate systems, the angular dependence of spin-orbit potential is further studied on fusion cross-sections.

Giant titanium electron wave function in gallium oxide: A potential electron-nuclear spin system for quantum information processing

NASA Astrophysics Data System (ADS)

Mentink-Vigier, Frédéric; Binet, Laurent; Vignoles, Gerard; Gourier, Didier; Vezin, Hervé

2010-11-01

The hyperfine interactions of the unpaired electron with eight surrounding G69a and G71a nuclei in Ti-doped β-Ga2O3 were analyzed by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopies. They are dominated by strong isotropic hyperfine couplings due to a direct Fermi contact interaction with Ga nuclei in octahedral sites of rutile-type chains oriented along b axis, revealing a large anisotropic spatial extension of the electron wave function. Titanium in β-Ga2O3 is thus best described as a diffuse (Ti4+-e-) pair rather than as a localized Ti3+ . Both electron and G69a nuclear spin Rabi oscillations could be observed by pulsed EPR and pulsed ENDOR, respectively. The electron spin decoherence time is about 1μs (at 4 K) and an upper bound of 520μs (at 8 K) is estimated for the nuclear decoherence time. Thus, β-Ga2O3:Ti appears to be a potential spin-bus system for quantum information processing with a large nuclear spin quantum register.

13C and 1H NMR (Nuclear Magnetic Resonance) studies of solid polyolefines

NASA Technical Reports Server (NTRS)

Cudby, M. E. A.; Harris, R. K.; Metcalfe, K.; Packer, K. J.; Smith, P. W. R.

1983-01-01

The basis of H-1 and C-13 high-resolution NMR investigations of solid polymers is outlined. The C-13 NMR spectra of solid syndiotactic and isotactic polypropene are discussed and their interpretation in terms of conformation and chain-packing effects are reviewed. The effects of decreasing temperature on the C-13 high-resolution spectrum of an annealed sample of isotactic polypropene is described and interpreted in terms of the crystal structure. The question of the proportion of the sample giving rise to C-13 signals is addressed and some results reported. The main cause for observing only part of the total sample is shown to be the H-1 rotating frame spin-lattice relaxation behavior. The H-1 spin-lattice relaxation and spectral characteristics of a number of polyolefin samples are summarized and the role of spin-diffusion discussed.

Discretization of the total magnetic field by the nuclear spin bath in fluorine-doped ZnSe.

PubMed

Zhukov, E A; Kirstein, E; Kopteva, N E; Heisterkamp, F; Yugova, I A; Korenev, V L; Yakovlev, D R; Pawlis, A; Bayer, M; Greilich, A

2018-05-16

The coherent spin dynamics of fluorine donor-bound electrons in ZnSe induced by pulsed optical excitation is studied in a perpendicular applied magnetic field. The Larmor precession frequency serves as a measure for the total magnetic field exerted onto the electron spins and, surprisingly, does not increase linearly with the applied field, but shows a step-like behavior with pronounced plateaus, given by multiples of the laser repetition rate. This discretization occurs by a feedback mechanism in which the electron spins polarize the nuclear spins, which in turn generate a local Overhauser field adjusting the total magnetic field accordingly. Varying the optical excitation power, we can control the plateaus, in agreement with our theoretical model. From this model, we trace the observed discretization to the optically induced Stark field, which causes the dynamic nuclear polarization.

Field-cycling NMR with high-resolution detection under magic-angle spinning: determination of field-window for nuclear hyperpolarization in a photosynthetic reaction center.

PubMed

Gräsing, Daniel; Bielytskyi, Pavlo; Céspedes-Camacho, Isaac F; Alia, A; Marquardsen, Thorsten; Engelke, Frank; Matysik, Jörg

2017-09-21

Several parameters in NMR depend on the magnetic field strength. Field-cycling NMR is an elegant way to explore the field dependence of these properties. The technique is well developed for solution state and in relaxometry. Here, a shuttle system with magic-angle spinning (MAS) detection is presented to allow for field-dependent studies on solids. The function of this system is demonstrated by exploring the magnetic field dependence of the solid-state photochemically induced nuclear polarization (photo-CIDNP) effect. The effect allows for strong nuclear spin-hyperpolarization in light-induced spin-correlated radical pairs (SCRPs) under solid-state conditions. To this end, 13 C MAS NMR is applied to a photosynthetic reaction center (RC) of the purple bacterium Rhodobacter (R.) sphaeroides wildtype (WT). For induction of the effect in the stray field of the magnet and its subsequent observation at 9.4 T under MAS NMR conditions, the sample is shuttled by the use of an aerodynamically driven sample transfer technique. In the RC, we observe the effect down to 0.25 T allowing to determine the window for the occurrence of the effect to be between about 0.2 and 20 T.

Microscopic study of spin cut-off factors of nuclear level densities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gholami, M.; Kildir, M.; Behkami, A. N.

Level densities and spin cut-off factors have been investigated within the microscopic approach based on the BCS Hamiltonian. In particular, the spin cut-off parameters have been calculated at neutron binding energies over a large range of nuclear mass using the BCS theory. The spin cut-off parameters {sigma}{sup 2}(E) have also been obtained from the Gilbert and Cameron expression and from rigid body calculations. The results were compared with their corresponding macroscopic values. It was found that the values of {sigma}{sup 2}(E) did not increase smoothly with A as expected based on macroscopic theory. Instead, the values of {sigma}{sup 2}(E) showmore » structure reflecting the angular momentum of the shell model orbitals near the Fermi energy.« less

Resonance-inclined optical nuclear spin polarization of liquids in diamond structures

NASA Astrophysics Data System (ADS)

Chen, Q.; Schwarz, I.; Jelezko, F.; Retzker, A.; Plenio, M. B.

2016-02-01

Dynamic nuclear polarization (DNP) of molecules in a solution at room temperature has the potential to revolutionize nuclear magnetic resonance spectroscopy and imaging. The prevalent methods for achieving DNP in solutions are typically most effective in the regime of small interaction correlation times between the electron and nuclear spins, limiting the size of accessible molecules. To solve this limitation, we design a mechanism for DNP in the liquid phase that is applicable for large interaction correlation times. Importantly, while this mechanism makes use of a resonance condition similar to solid-state DNP, the polarization transfer is robust to a relatively large detuning from the resonance due to molecular motion. We combine this scheme with optically polarized nitrogen-vacancy (NV) center spins in nanodiamonds to design a setup that employs optical pumping and is therefore not limited by room temperature electron thermal polarization. We illustrate numerically the effectiveness of the model in a flow cell containing nanodiamonds immobilized in a hydrogel, polarizing flowing water molecules 4700-fold above thermal polarization in a magnetic field of 0.35 T, in volumes detectable by current NMR scanners.

Analytic treatment of nuclear spin-lattice relaxation for diffusion in a cone model

NASA Astrophysics Data System (ADS)

Sitnitsky, A. E.

2011-12-01

We consider nuclear spin-lattice relaxation rate resulted from a diffusion equation for rotational wobbling in a cone. We show that the widespread point of view that there are no analytical expressions for correlation functions for wobbling in a cone model is invalid and prove that nuclear spin-lattice relaxation in this model is exactly tractable and amenable to full analytical description. The mechanism of relaxation is assumed to be due to dipole-dipole interaction of nuclear spins and is treated within the framework of the standard Bloemberger, Purcell, Pound-Solomon scheme. We consider the general case of arbitrary orientation of the cone axis relative the magnetic field. The BPP-Solomon scheme is shown to remain valid for systems with the distribution of the cone axes depending only on the tilt relative the magnetic field but otherwise being isotropic. We consider the case of random isotropic orientation of cone axes relative the magnetic field taking place in powders. Also we consider the cases of their predominant orientation along or opposite the magnetic field and that of their predominant orientation transverse to the magnetic field which may be relevant for, e.g., liquid crystals. Besides we treat in details the model case of the cone axis directed along the magnetic field. The latter provides direct comparison of the limiting case of our formulas with the textbook formulas for free isotropic rotational diffusion. The dependence of the spin-lattice relaxation rate on the cone half-width yields results similar to those predicted by the model-free approach.

Detection of C-13O radio emission from C-13-rich carbon stars

NASA Technical Reports Server (NTRS)

Jura, M.; Kahane, C.; Omont, A.

1988-01-01

A high ratio of C-13O radio emission in the J = 1-0 rotational line has been detected from three mass-losing carbon stars which optical data indicate have high C-13/C12 ratios. Since chemical fractionation, isotope-dependent photodissociation and opacity in the rotational and vibrational lines may not raise significantly the C-13O ratio above the actual C-13/C-12 ratio in these circumstellar envelopes, the relative abundance of C-13 in these stars might be even greater by perhaps a factor of two than previously believed. About 15 percent of all luminous carbon stars are C-13-rich, and these stars may play a significant role in the enhancement in the C-13/C12 ratio that has occurred during the past 4.6 billion years since the formation of the sun.

Directing Nuclear Spin Flips in InAs Quantum Dots Using Detuned Optical Pulse Trains

DTIC Science & Technology

2009-04-24

Directing Nuclear Spin Flips in InAs Quantum Dots Using Detuned Optical Pulse Trains S . G. Carter,1 A. Shabaev,2 Sophia E. Economou,1 T. A. Kennedy,1...A. S . Bracker,1 and T. L. Reinecke1 1Naval Research Laboratory, Washington, D.C. 20375-5322, USA 2School of Computational Sciences, George Mason...trion spin states and the allowed transitions. Single (double) arrows are electron (hole) spins. PRL 102, 167403 (2009) P HY S I CA L R EV I EW LE T T ER

Effects of nuclear structure in the spin-dependent scattering of weakly interacting massive particles

NASA Astrophysics Data System (ADS)

Nikolaev, M. A.; Klapdor-Kleingrothaus, H. V.

1993-06-01

We present calculations of the nuclear from factors for spin-dependent elastic scattering of dark matter WIMPs from123Te and131Xe isotopes, proposed to be used for dark matter detection. A method based on the theory of finite Fermi systems was used to describe the reduction of the single-particle spin-dependent matrix elements in the nuclear medium. Nucleon single-particle states were calculated in a realistic shell model potential; pairing effects were treated within the BCS model. The coupling of the lowest single-particle levels in123Te to collective 2+ excitations of the core was taken into account phenomenologically. The calculated nuclear form factors are considerably less then the single-particle ones for low momentum transfer. At high momentum transfer some dynamical amplification takes place due to the pion exchange term in the effective nuclear interaction. But as the momentum transfer increases, the difference disappears, the momentum transfer increases and the quenching effect disappears. The shape of the nuclear form factor for the131Xe isotope differs from the one obtained using an oscillator basis.

Methyl fluoride-13C in nematic liquid crystals: Anisotropy of the indirect 13C-19F spin-spin coupling and of the 1H, 13C, and 19F chemical shieldings

NASA Astrophysics Data System (ADS)

Jokisaari, J.; Hiltunen, Y.; Lounila, J.

1986-09-01

The anisotropy of the indirect 13C-19F spin-spin coupling tensor of methyl fluoride-13C in the liquid crystals ZLI 1167, EBBA, their mixtures, phase IV, and phase 1221 was studied by applying 1H and 19F NMR spectroscopy. The relative anisotropy ΔJCF/JCF gets values between -4.3 (in ZLI 1167) and +30.7 (in EBBA) when determined in the conventional way from the experimental dipolar coupling constants taking into account only harmonic vibrational corrections. The inclusion of the deformational corrections in both the direct and indirect C-F coupling tensors leads to a constant, solvent independent relative anisotropy of -2.5±0.2. This result is also obtained when a mixture of the liquid crystals ZLI 1167 and EBBA is used which mixture gives an undistorted geometry for methyl fluoride. The chemical shielding anisotropies ΔσH, ΔσC, and ΔσF for methyl fluoride were determined by applying the method of mixing two thermotropic nematogens (ZLI 1167 and EBBA) with opposite anisotropies of diamagnetic susceptibility. The results ΔσH =+5.2±0.2 ppm, ΔσC =+87±4 ppm, and ΔσF =-90±4 ppm are in fair agreement with theoretical calculations.

Properties of K,Rb-intercalated C{sub 60} encapsulated inside carbon nanotubes called peapods derived from nuclear magnetic resonance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahfouz, R.; Bouhrara, M.; Kim, Y.

2015-09-21

We present a detailed experimental study on how magnetic and electronic properties of Rb,K-intercalated C{sub 60} encapsulated inside carbon nanotubes called peapods can be derived from {sup 13}C nuclear magnetic resonance investigations. Ring currents do play a basic role in those systems; in particular, the inner cavities of nanotubes offer an ideal environment to investigate the magnetism at the nanoscale. We report the largest diamagnetic shifts down to −68.3 ppm ever observed in carbon allotropes, which is connected to the enhancement of the aromaticity of the nanotube envelope upon intercalation. The metallization of intercalated peapods is evidenced from the chemical shiftmore » anisotropy and spin-lattice relaxation (T{sub 1}) measurements. The observed relaxation curves signal a three-component model with two slow and one fast relaxing components. We assigned the fast component to the unpaired electrons charged C{sub 60} that show a phase transition near 100 K. The two slow components can be rationalized by the two types of charged C{sub 60} at two different positions with a linear regime following Korringa behavior, which is typical for metallic system and allow us to estimate the density of sate at Fermi level n(E{sub F})« less

Optical pumping of the electronic and nuclear spin of single charge-tunable quantum dots.

PubMed

Bracker, A S; Stinaff, E A; Gammon, D; Ware, M E; Tischler, J G; Shabaev, A; Efros, Al L; Park, D; Gershoni, D; Korenev, V L; Merkulov, I A

2005-02-04

We present a comprehensive examination of optical pumping of spins in individual GaAs quantum dots as we change the net charge from positive to neutral to negative with a charge-tunable heterostructure. Negative photoluminescence polarization memory is enhanced by optical pumping of ground state electron spins, which we prove with the first measurements of the Hanle effect on an individual quantum dot. We use the Overhauser effect in a high longitudinal magnetic field to demonstrate efficient optical pumping of nuclear spins for all three charge states of the quantum dot.

Optical Pumping of the Electronic and Nuclear Spin of Single Charge-Tunable Quantum Dots

NASA Astrophysics Data System (ADS)

Bracker, A. S.; Stinaff, E. A.; Gammon, D.; Ware, M. E.; Tischler, J. G.; Shabaev, A.; Efros, Al. L.; Park, D.; Gershoni, D.; Korenev, V. L.; Merkulov, I. A.

2005-02-01

We present a comprehensive examination of optical pumping of spins in individual GaAs quantum dots as we change the net charge from positive to neutral to negative with a charge-tunable heterostructure. Negative photoluminescence polarization memory is enhanced by optical pumping of ground state electron spins, which we prove with the first measurements of the Hanle effect on an individual quantum dot. We use the Overhauser effect in a high longitudinal magnetic field to demonstrate efficient optical pumping of nuclear spins for all three charge states of the quantum dot.

Improved characterization of the botanical origin of sugar by carbon-13 SNIF-NMR applied to ethanol.

PubMed

Thomas, Freddy; Randet, Celia; Gilbert, Alexis; Silvestre, Virginie; Jamin, Eric; Akoka, Serge; Remaud, Gerald; Segebarth, Nicolas; Guillou, Claude

2010-11-24

Until now, no analytical method, not even isotopic ones, had been able to differentiate between sugars coming from C4-metabolism plants (cane, maize, etc.) and some crassulacean acid metabolism plants (e.g., pineapple, agave) because in both cases the isotope distributions of the overall carbon-13/carbon-12 and site-specific deuterium/hydrogen isotope ratios are very similar. Following recent advances in the field of quantitative isotopic carbon-13 NMR measurements, a procedure for the analysis of the positional carbon-13/carbon-12 isotope ratios of ethanol derived from the sugars of pineapples and agave using the site-specific natural isotopic fractionation-nuclear magnetic resonance (SNIF-NMR) method is presented. It is shown that reproducible results can be obtained when appropriate analytical conditions are used. When applied to pineapple juice, this new method demonstrates a unique ability to detect cane and maize sugar, which are major potential adulterants, with a detection limit in the order of 15% of the total sugars, which provides an efficient mean of controlling the authenticity of juices made from this specific fruit. When applied to tequila products, this new method demonstrates a unique ability to unambiguously differentiate authentic 100% agave tequila, as well as misto tequila (made from at least 51% agave), from products made from a larger proportion of cane or maize sugar and therefore not complying with the legal definition of tequila.

How to Calculate Spin-Spin Coupling and Spin-Rotation Coupling Strengths and Their Uncertainties from Spectroscopic Data: Application to the c(1^3Σ_g^+) State of Diatomic Lithium

NASA Astrophysics Data System (ADS)

Dattani, Nikesh S.; Li, Xuan

2013-06-01

Recent high-resolution (± 0.00002 cm^{-1}) photo-association spectroscopy (PAS) data of seven previously unexplored vibrational levels of the 1^3Σ_g^+ state of Li_2 have allowed for the first ever experimental determination of the spin-spin (λ_v) and spin-rotation (γ_v) coupling constants in a diatomic lithium system. For triplet states of diatomic molecules such as the 1^3Σ_g^+ state of Li_2, the three spin-spin/spin-rotation resolved energies associated with a ro-vibrational state |v,N> were expressed explicity in terms of B_v, λ_v, and γ_v in 1929 by Kramer's first-order formulas and then in 1937 by Schlapp's more refined formulas. Given spectroscopic data, while it has never been difficult to extract λ_v and γ_v from Schlapp's formulas, it has been a challenge to reliably predict how accurate these extracted values are. This is for two reasons: (1) the lack of a rigorous method to estimate the uncertainty in B_v, (2) the non-linearity of Schlapp's coupled equations has meant that traditionally they have had to be solved numerically by Newton iterations which makes error propagation difficult. The former challenge has been this year solved by Le Roy with a modification of Hutson's perturbation theory of, and the latter problem has now been solved by symbolic computing software that solves Schlapp's coupled non-linear equations analytically for the first time since their introduction in 1937. M. Semczuk, X. Li, W. Gunton, M. Haw, N. Dattani, J. Witz, A. Mills, D. Jones, K. Madison, Physical Review A {87}, XX (2013) H. Kramers, Zeitschrift fur Physik {53}, 422 (1929) R. Schlapp, Physical Review {51}, 342 (1937) J. Hutson, J. Phys. B, {14}, 851 (1981)

Spectroscopic Measurement of LEAD-204 Isotope Shift and LEAD-205 Nuclear Spin.

NASA Astrophysics Data System (ADS)

Schonberger, Peter

The isotope shift of ('204)Pb and the nuclear spin of 1.4 x 10('7)-y ('205)Pb was determined from a high -resolution optical measurement of the 6p('2) ('3)P(,o) -6p7s('3)P(,1)('o) 283.3-nm resonance line. The value of the shift, relative to ('208)Pb is -140.2(8) x 10('-3)cm(' -1), the negative sign indicating a shift to lower wave numbers. The precision is 3-4 times greater than that of previous measurements. The spin of ('205)Pb l = 5/2 was obtained from the measurement of the relative intensities of its three hyperfine components. This method of absorption spectroscopy determination of ground state nuclear spin is applicable to any stable or longlived isotope. High resolution optical absorption spectra were obtained with a 25.4cm diffraction grating in a 9.1m focal length Czerny-Turner spectrometer. A signal-averaging scanning technique was used to record the spectra. Increased precision in the isotope shift measurement was attained by using separated isotope samples of ('204)Pb and ('207)Pb. A controlled amount of the later was incorporated in the absorption cell to provide internal calibration by its 6p7s ('3)P(,1)('o) hfs separation. Absorption spectra were recorded for several optical thicknesses of the absorber. A single spin value of increased precision was derived from the entire set of combined data.

Sealed magic angle spinning nuclear magnetic resonance probe and process for spectroscopy of hazardous samples

DOEpatents

Cho, Herman M.; Washton, Nancy M.; Mueller, Karl T.; Sears, Jr., Jesse A.; Townsend, Mark R.; Ewing, James R.

2016-06-14

A magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) probe is described that includes double containment enclosures configured to seal and contain hazardous samples for analysis. The probe is of a modular design that ensures containment of hazardous samples during sample analysis while preserving spin speeds for superior NMR performance and convenience of operation.

Estimated lag time in global carbon emissions and CO2 concentrations produced by commercial nuclear power through 2009 with projections through 2030.

PubMed

Coleman, Neil M; Abramson, Lee R; Coleman, Fiona A B

2012-03-01

This study examines the past and future impact of nuclear reactors on anthropogenic carbon emissions to the atmosphere. If nuclear power had never been commercially developed, what additional global carbon emissions would have occurred? More than 44 y of global nuclear power have caused a lag time of at least 1.2 y in carbon emissions and CO2 concentrations through the end of 2009. This lag time incorporates the contribution of life cycle carbon emissions due to the construction and operation of nuclear plants. Cumulative global carbon emissions would have been about 13 Gt greater through 2009, and the mean annual CO2 concentration at Mauna Loa would have been ~2.7 ppm greater than without nuclear power. This study finds that an additional 14–17 Gt of atmospheric carbon emissions could be averted by the global use of nuclear power through 2030, for a cumulative total of 27–30 Gt averted during the period 1965–2030. This result is based on International Atomic Energy Agency projections of future growth in nuclear power from 2009–2030, modified by the recent loss or permanent shutdown of 14 reactors in Japan and Germany

Carbon-related platinum defects in silicon: An electron paramagnetic resonance study of high spin states

NASA Astrophysics Data System (ADS)

Scheerer, O.; Höhne, M.; Juda, U.; Riemann, H.

1997-10-01

In this article, we report about complexes in silicon investigated by electron paramagnetic resonance (EPR). In silicon doped with C and Pt we detected two different complexes: cr-1Pt (cr: carbon-related, 1Pt: one Pt atom) and cr-3Pt. The complexes have similar EPR properties. They show a trigonal symmetry with effective g-values geff,⊥=2g⊥≈4 and geff,‖=g‖≈2 (g⊥, g‖ true g-values). The g-values can be explained by a spin Hamiltonian with large fine-structure energy (electron spin S=3/2) and smaller Zeeman interaction. The participation of platinum in the complexes is proved by the hyperfine interaction. From experiments with varying carbon concentration we conclude that the complexes contain carbon. Atomistic models based on the Watkins vacancy-model for substitutional Pt were developed.

Carbon-13 and carbon-14 labeled dabigatran etexilate and tritium labeled dabigatran.

PubMed

Latli, Bachir; Kiesling, Ralf; Aßfalg, Stefan; Chevliakov, Max; Hrapchak, Matt; Campbell, Scot; Gonnella, Nina; Busacca, Carl A; Senanayake, Chris H

2016-12-01

Dabigatran etexilate or pradaxa, a novel oral anticoagulant, is a reversible, competitive, direct thrombin inhibitor. It is used to prevent strokes in patients with atrial fibrillation and the formation of blood clots in the veins (deep venous thrombosis) in adults who have had an operation to replace a hip or a knee. Pradaxa is the only novel oral anticoagulant available with both proven superiority to warfarin and a specific reversal agent for use in rare emergency situations. The detailed description of the synthesis of carbon-13 and carbon-14 labeled dabigatran etexilate, and tritium labeled dabigatran is described. The synthesis of carbon-13 dabigatran etexilate was accomplished in eight steps and in 6% overall yield starting from aniline- 13 C 6 . Ethyl bromoacetate-1- 14 C was the reagent of choice in the synthesis of carbon-14 labeled dabigatran etexilate in six steps and 17% overall yield. Tritium labeled dabigatran was prepared using either direct tritium incorporation under Crabtree's catalytic conditions or tritium-dehalogenation of a diiodo-precursor of dabigatran. Copyright © 2016 John Wiley & Sons, Ltd.

Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state 13C nuclear magnetic resonance spectroscopy

USGS Publications Warehouse

Cao, X.; Mastalerz, Maria; Chappell, M.A.; Miller, L.F.; Li, Y.; Mao, J.

2011-01-01

Four lithotypes (vitrain, bright clarain, clarain, and fusain) of a high volatile bituminous Springfield Coal from the Illinois Basin were characterized using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The NMR techniques included quantitative direct polarization/magic angle spinning (DP/MAS), cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CHn selection, and recoupled C-H long-range dipolar dephasing techniques. The lithotypes that experienced high-pressure CO2 adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO2 saturation at high pressure and subsequent evacuation. The main carbon functionalities present in original vitrain, bright clarain, clarain and fusain were aromatic carbons (65.9%-86.1%), nonpolar alkyl groups (9.0%-28.9%), and aromatic C-O carbons (4.1%-9.5%). Among these lithotypes, aromaticity increased in the order of clarain, bright clarain, vitrain, and fusain, whereas the fraction of alkyl carbons decreased in the same order. Fusain was distinct from other three lithotypes in respect to its highest aromatic composition (86.1%) and remarkably small fraction of alkyl carbons (11.0%). The aromatic cluster size in fusain was larger than that in bright clarain. The lithotypes studied responded differently to high pressure CO2 saturation. After exposure to high pressure CO2, vitrain and fusain showed a decrease in aromaticity but an increase in the fraction of alkyl carbons, whereas bright clarain and clarain displayed an increase in aromaticity but a decrease in the fraction of alkyl carbons. Aromatic fused-rings were larger for bright clarain but smaller for fusain in the post-CO2 adsorption samples compared to the original lithotypes. These observations suggested chemical CO2-coal interactions at high pressure and the selectivity of lithotypes in response to CO2 adsorption. ?? 2011 Elsevier B.V.

Revisiting spin-lattice relaxation time measurements for dilute spins in high-resolution solid-state NMR spectroscopy

NASA Astrophysics Data System (ADS)

Fu, Riqiang; Li, Jun; Cui, Jingyu; Peng, Xinhua

2016-07-01

Numerous nuclear magnetic resonance (NMR) measurements of spin-lattice relaxation times (T1S) for dilute spins such as 13C have led to investigations of the motional dynamics of individual functional groups in solid materials. In this work, we revisit the Solomon equations and analyze how the heteronuclear cross relaxation between the dilute S (e.g. 13C) and abundant I (e.g. 1H) spins affects the measured T1S values in solid-state NMR in the absence of 1H saturation during the recovery time. It is found theoretically that at the beginning of the S spin magnetization recovery, the existence of non-equilibrium I magnetization introduces the heteronuclear cross relaxation effect onto the recovery of the S spin magnetization and confirmed experimentally that such a heteronuclear cross relaxation effect results in the recovery overshoot phenomena for the dilute spins when T1S is on the same order of T1H, leading to inaccurate measurements of the T1S values. Even when T1S is ten times larger than T1H, the heteronuclear cross relaxation effect on the measured T1S values is still noticeable. Furthermore, this cross relaxation effect on recovery trajectory of the S spins can be manipulated and even suppressed by preparing the initial I and S magnetization, so as to obtain the accurate T1S values. A sample of natural abundance L-isoleucine powder has been used to demonstrate the T1S measurements and their corresponding measured T1C values under various experimental conditions.

Long coherence times in nuclear spin-free vanadyl qubits [Long coherence times in surface-compatible nuclear spin-free vanadium qubits

DOE PAGES

Yu, Chung -Jui; Graham, Michael J.; Zadrozny, Joseph M.; ...

2016-10-31

Quantum information processing (QIP) offers the potential to create new frontiers in fields ranging from quantum biology to cryptography. Two key figures of merit for electronic spin qubits, the smallest units of QIP, are the coherence time ( T2), the lifetime of the qubit, and the spin–lattice relaxation time ( T1), the thermally defined upper limit of T2. To achieve QIP, processable qubits with long coherence times are required. Recent studies on (Ph4P-d20)2[V(C8S8)3], a vanadium-based qubit, demonstrate that millisecond T2 times are achievable in transition metal complexes with nuclear spinfree environments. Applying these principles to vanadyl complexes offers a routemore » to combine the previously established surface compatibility of the flatter vanadyl structures with a long T2. Toward those ends, we investigated a series of four qubits, (Ph 4P) 2[VO(C 8S 8) 2] (1), (Ph 4P) 2[VO(β-C 3S 5) 2] (2), (Ph 4P) 2[VO(α-C 3S 5) 2] (3), and (Ph 4P) 2[VO(C 3S 4O) 2] (4), by pulsed electron paramagnetic resonance (EPR) spectroscopy and compared the performance of these species with our recently reported set of vanadium tris(dithiolene) complexes. Crucially we demonstrate that solutions of 1–4 in SO 2, a uniquely polar nuclear spinfree solvent, reveal T2 values of up to 152(6) μs, comparable to the best molecular qubit candidates. Upon transitioning to vanadyl species from the tris(dithiolene) analogues, we observe a remarkable order of magnitude increase in 12, attributed to stronger solute–solvent interactions with the polar vanadium-oxo moiety. Simultaneously, we detect a small decrease in T2 for the vanadyl analogues relative to the tris(dithiolene) complexes. We attribute this decrease to the absence of one nuclear spinfree ligand, which served to shield the vanadium centers against solvent nuclear spins. Lastly, our results highlight new design principles for long T1 and T2 times by demonstrating the efficacy of ligand-based tuning of solute�

Nuclear Spin Dependent Parity Violation in Diatomic Molecules

NASA Astrophysics Data System (ADS)

Cahn, Sidney; Altuntas, Emine; Ammon, Jeffrey; Demille, David

2015-10-01

Nuclear spin-dependent parity violation (NSD-PV) effects arise from the exchange of the Z0 boson between electrons and the nucleus and from the interaction of electrons with the nuclear anapole moment, a parity-odd magnetic moment. The anapole moment grows as A2/3 of the nucleus,while the Z0 coupling is independent of A. We study NSD-PV effects using diatomic molecules, where signals are dramatically amplified by bringing rotational levels of opposite parity close to degeneracy in a strong magnetic field. Using a Stark-interference technique, we measure the NSD-PV interaction matrix element. We present results that demonstrate statistical sensitivity to NSD-PV effects surpassing that of any previous atomic parity violation measurement, using the test system 138Ba19F. We also discuss improvements on investigations of systematics due to non-reversing stray E-fields, Enr together with B-field inhomogeneities, and short-term prospects for measuring the nuclear anapole moment of 137Ba. In the long term, our technique is sufficiently general and sensitive to enable measurements across a broad range of nuclei.

Carbon pricing, nuclear power and electricity markets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cameron, R.; Keppler, J. H.

2012-07-01

In 2010, the NEA in conjunction with the International Energy Agency produced an analysis of the Projected Costs of Electricity for almost 200 power plants, covering nuclear, fossil fuel and renewable electricity generation. That analysis used lifetime costs to consider the merits of each technology. However, the lifetime cost analysis is less applicable in liberalised markets and does not look specifically at the viewpoint of the private investor. A follow-up NEA assessment of the competitiveness of nuclear energy against coal- and gas-fired generation under carbon pricing has considered just this question. The economic competition in electricity markets is today betweenmore » nuclear energy and gas-fired power generation, with coal-fired power generation not being competitive as soon as even modest carbon pricing is introduced. Whether nuclear energy or natural gas comes out ahead in their competition depends on a number of assumptions, which, while all entirely reasonable, yield very different outcomes. The analysis in this study has been developed on the basis of daily data from European power markets over the last five-year period. Three different methodologies, a Profit Analysis looking at historic returns over the past five years, an Investment Analysis projecting the conditions of the past five years over the lifetime of plants and a Carbon Tax Analysis (differentiating the Investment Analysis for different carbon prices) look at the issue of competitiveness from different angles. They show that the competitiveness of nuclear energy depends on a number of variables which in different configurations determine whether electricity produced from nuclear power or from CCGTs generates higher profits for its investors. These are overnight costs, financing costs, gas prices, carbon prices, profit margins (or mark-ups), the amount of coal with carbon capture and electricity prices. This paper will present the outcomes of the analysis in the context of a

An elementary quantum network using robust nuclear spin qubits in diamond

NASA Astrophysics Data System (ADS)

Kalb, Norbert; Reiserer, Andreas; Humphreys, Peter; Blok, Machiel; van Bemmelen, Koen; Twitchen, Daniel; Markham, Matthew; Taminiau, Tim; Hanson, Ronald

Quantum registers containing multiple robust qubits can form the nodes of future quantum networks for computation and communication. Information storage within such nodes must be resilient to any type of local operation. Here we demonstrate multiple robust memories by employing five nuclear spins adjacent to a nitrogen-vacancy defect centre in diamond. We characterize the storage of quantum superpositions and their resilience to entangling attempts with the electron spin of the defect centre. The storage fidelity is found to be limited by the probabilistic electron spin reset after failed entangling attempts. Control over multiple memories is then utilized to encode states in decoherence protected subspaces with increased robustness. Furthermore we demonstrate memory control in two optically linked network nodes and characterize the storage capabilities of both memories in terms of the process fidelity with the identity. These results pave the way towards multi-qubit quantum algorithms in a remote network setting.

Functionalizing carbon nitride with heavy atom-free spin converters for enhanced 1 O 2 generation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Wenting; Han, Congcong; Zhang, Qinhua

advanced photosensitizers for singlet oxygen (1O2) generation. However, the intersystem crossing (ISC) process is quite insufficient in carbon nitride, limiting the 1O2 generation. Here, we report a facile and general strategy to confined benzophenone as a heavy atom-free spin converter dopant in carbon nitride via the facile copolymerization. With proper energy level matching between the heavy atom-free spin converter and various ligands based on carbon nitride precursors, the proper combination can decrease the singlet-triplet energy gap (DEST) and hence generate 1O2 effectively. Due to its significant and selectivity for 1O2 generation, the as-prepared carbon nitride-based photosensitizer shows a high selectivemore » photooxidation activity for 1,5-dihydroxy-naphthalene (1,5-DHN). The product yield reached 71.8% after irradiation for 60 min, which was higher than that of cyclometalated PtII complexes (53.6%) in homogeneous photooxidation. This study can broaden the application of carbon nitride in the field of selective heterogeneous photooxidation due to simple operation, low cost, and high efficiency, making it a strong candidate for future industrialization.« less

Persistent Optical Nuclear Spin Narrowing in a Singly Charged InAs Quantum Dot

DTIC Science & Technology

2012-02-01

explained in terms of an anisotropic hyperfine coupling between the hole spin and the nuclear spins. © 2012 Optical Society of America OCIS codes: 300.6250...February 2012 / J. Opt. Soc. Am. B A121 where γs (γt) is the spin (trion) dephasing rate, χ is half the pump Rabi frequency ΩR (ΩR # μEℏ , where μ is...probe ab- sorption at the dark state dip (αdip) and the Rabi sideband (αpeak): αdip # α0 χ2γs & γt$γ2s% χ4 & 2χ2γtγs & γ2t γ2s ; (11) αpeak # α0 χ2γs

Unifying the rotational and permutation symmetry of nuclear spin states: Schur-Weyl duality in molecular physics.

PubMed

Schmiedt, Hanno; Jensen, Per; Schlemmer, Stephan

2016-08-21

In modern physics and chemistry concerned with many-body systems, one of the mainstays is identical-particle-permutation symmetry. In particular, both the intra-molecular dynamics of a single molecule and the inter-molecular dynamics associated, for example, with reactive molecular collisions are strongly affected by selection rules originating in nuclear-permutation symmetry operations being applied to the total internal wavefunctions, including nuclear spin, of the molecules involved. We propose here a general tool to determine coherently the permutation symmetry and the rotational symmetry (associated with the group of arbitrary rotations of the entire molecule in space) of molecular wavefunctions, in particular the nuclear-spin functions. Thus far, these two symmetries were believed to be mutually independent and it has even been argued that under certain circumstances, it is impossible to establish a one-to-one correspondence between them. However, using the Schur-Weyl duality theorem we show that the two types of symmetry are inherently coupled. In addition, we use the ingenious representation-theory technique of Young tableaus to represent the molecular nuclear-spin degrees of freedom in terms of well-defined mathematical objects. This simplifies the symmetry classification of the nuclear wavefunction even for large molecules. Also, the application to reactive collisions is very straightforward and provides a much simplified approach to obtaining selection rules.

Unifying the rotational and permutation symmetry of nuclear spin states: Schur-Weyl duality in molecular physics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmiedt, Hanno; Schlemmer, Stephan; Jensen, Per, E-mail: jensen@uni-wuppertal.de

In modern physics and chemistry concerned with many-body systems, one of the mainstays is identical-particle-permutation symmetry. In particular, both the intra-molecular dynamics of a single molecule and the inter-molecular dynamics associated, for example, with reactive molecular collisions are strongly affected by selection rules originating in nuclear-permutation symmetry operations being applied to the total internal wavefunctions, including nuclear spin, of the molecules involved. We propose here a general tool to determine coherently the permutation symmetry and the rotational symmetry (associated with the group of arbitrary rotations of the entire molecule in space) of molecular wavefunctions, in particular the nuclear-spin functions. Thusmore » far, these two symmetries were believed to be mutually independent and it has even been argued that under certain circumstances, it is impossible to establish a one-to-one correspondence between them. However, using the Schur-Weyl duality theorem we show that the two types of symmetry are inherently coupled. In addition, we use the ingenious representation-theory technique of Young tableaus to represent the molecular nuclear-spin degrees of freedom in terms of well-defined mathematical objects. This simplifies the symmetry classification of the nuclear wavefunction even for large molecules. Also, the application to reactive collisions is very straightforward and provides a much simplified approach to obtaining selection rules.« less

Spinning, structure and properties of PP/CNTs and PP/carbon black composite fibers

NASA Astrophysics Data System (ADS)

Marcincin, A.; Hricova, M.; Ujhelyiova, A.

2014-08-01

In this paper, the effect of the compatibilisers-dispersants and other nanofillers on melt spinning of the polypropylene (PP) composites, containing carbon nanotubes (CNTs), and carbon black pigment (CBP) has been investigated. Further, the structure and selected properties of composite fibers, such as mechanical and electrical have been studied. The results revealed, that percolation threshold for PP/CBP composite fibres was situated within the concentration of 15 - 20 wt%, what is several times higher than for PP/CNTs fibers.

Analysis of the Electronic Structure of the Special Pair of a Bacterial Photosynthetic Reaction Center by 13 C Photochemically Induced Dynamic Nuclear Polarization Magic-Angle Spinning NMR Using a Double-Quantum Axis.

PubMed

Najdanova, Marija; Gräsing, Daniel; Alia, A; Matysik, Jörg

2018-01-01

The origin of the functional symmetry break in bacterial photosynthesis challenges since several decades. Although structurally very similar, the two branches of cofactors in the reaction center (RC) protein complex act very differently. Upon photochemical excitation, an electron is transported along one branch, while the other remains inactive. Photochemically induced dynamic nuclear polarization (photo-CIDNP) magic-angle spinning (MAS) 13 C NMR revealed that the two bacteriochlorophyll cofactors forming the "Special Pair" donor dimer are already well distinguished in the electronic ground state. These previous studies are relying solely on 13 C- 13 C correlation experiments as radio-frequency-driven recoupling (RFDR) and dipolar-assisted rotational resonance (DARR). Obviously, the chemical-shift assignment is difficult in a dimer of tetrapyrrole macrocycles, having eight pyrrole rings of similar chemical shifts. To overcome this problem, an INADEQUATE type of experiment using a POST C7 symmetry-based approach is applied to selectively isotope-labeled bacterial RC of Rhodobacter (R.) sphaeroides wild type (WT). We, therefore, were able to distinguish unresolved sites of the macromolecular dimer. The obtained chemical-shift pattern is in-line with a concentric assembly of negative charge within the common center of the Special Pair supermolecule in the electronic ground state. © 2017 The American Society of Photobiology.

Hyperpolarized 13C NMR lifetimes in the liquid-state: relating structures and T1 relaxation times

NASA Astrophysics Data System (ADS)

Parish, Christopher; Niedbalski, Peter; Hashami, Zohreh; Fidelino, Leila; Kovacs, Zoltan; Lumata, Lloyd

Among the various attempts to solve the insensitivity problem in nuclear magnetic resonance (NMR), the physics-based technique dissolution dynamic nuclear polarization (DNP) is probably the most successful method of hyperpolarization or amplifying NMR signals. Using this technique, liquid-state NMR signal enhancements of several thousand-fold are expected for low-gamma nuclei such as carbon-13. The lifetimes of these hyperpolarized 13C NMR signals are directly related to their 13C spin-lattice relaxation times T1. Depending upon the 13C isotopic location, the lifetimes of hyperpolarized 13C compounds can range from a few seconds to minutes. In this study, we have investigated the hyperpolarized 13C NMR lifetimes of several 13C compounds with various chemical structures from glucose, acetate, citric acid, naphthalene to tetramethylallene and their deuterated analogs at 9.4 T and 25 deg C. Our results show that the 13C T1s of these compounds can range from a few seconds to more than 60 s at this field. Correlations between the chemical structures and T1 relaxation times will be discussed and corresponding implications of these results on 13C DNP experiments will be revealed. US Dept of Defense Award No. W81XWH-14-1-0048 and Robert A. Welch Foundation Grant No. AT-1877.

Liquid and gas phase NMR spectra of 13CH313CHO acetaldehyde

NASA Astrophysics Data System (ADS)

Makulski, Włodzimierz; Wikieł, Agata J.

2018-01-01

The gas phase NMR experiments perform a vital role in establishing the magnetic shielding and spin-spin coupling constants which are free from intermolecular interactions, equivalent to the parameter of isolated molecules. This work is concerned with an acetaldehyde molecule. Small amounts of acetaldehyde 13CH313CHO in gaseous matrices of CO2 and Xe were studied using high-precision 1H and 13C NMR measurements. Results were extrapolated to the zero-density limit permitting the determinations of the 1H and 13C absolute nuclear magnetic shielding of an isolated acetaldehyde molecule. The difference between the experimental and recent theoretical DFT results is discussed. Several samples of 13CH313CHO dissolved in popular organic and inorganic solvents were also investigated. Gas-to-solution shifts show the influence of the association process when acetaldehyde is transferred from gas to liquid state. Several spin-spin coupling constants in the gas phase and in different solvents were precisely measured.

Spin-Mechatronics

NASA Astrophysics Data System (ADS)

Matsuo, Mamoru; Saitoh, Eiji; Maekawa, Sadamichi

2017-01-01

We investigate the interconversion phenomena between spin and mechanical angular momentum in moving objects. In particular, the recent results on spin manipulation and spin-current generation by mechanical motion are examined. In accelerating systems, spin-dependent gauge fields emerge, which enable the conversion from mechanical angular momentum into spins. Such a spin-mechanical effect is predicted by quantum theory in a non-inertial frame. Experiments which confirm the effect, i.e., the resonance frequency shift in nuclear magnetic resonance, the stray field measurement of rotating metals, and electric voltage generation in liquid metals, are discussed.

Amplification of Dynamic Nuclear Polarization at 200 GHz by Arbitrary Pulse Shaping of the Electron Spin Saturation Profile.

PubMed

Kaminker, Ilia; Han, Songi

2018-06-07

Dynamic nuclear polarization (DNP) takes center stage in nuclear magnetic resonance (NMR) as a tool to amplify its signal by orders of magnitude through the transfer of polarization from electron to nuclear spins. In contrast to modern NMR and electron paramagnetic resonance (EPR) that extensively rely on pulses for spin manipulation in the time domain, the current mainstream DNP technology exclusively relies on monochromatic continuous wave (CW) irradiation. This study introduces arbitrary phase shaped pulses that constitute a train of coherent chirp pulses in the time domain at 200 GHz (7 T) to dramatically enhance the saturation bandwidth and DNP performance compared to CW DNP, yielding up to 500-fold in NMR signal enhancements. The observed improvement is attributed to the recruitment of additional electron spins contributing to DNP via the cross-effect mechanism, as experimentally confirmed by two-frequency pump-probe electron-electron double resonance (ELDOR).

Nuclear Spin Dependent Parity Violation in Diatomic Molecules

NASA Astrophysics Data System (ADS)

Altuntas, Emine; Ammon, Jeffrey; Cahn, Sidney; Demille, David; Kozlov, Mikhail; Paolino, Richard

2015-05-01

Nuclear spin-dependent parity violation (NSD-PV) effects arise from exchange of the Z0 boson between electrons and the nucleus, and from interaction of electrons with the nuclear anapole moment, a parity-odd magnetic moment. The latter scales with nucleon number of the nucleus A as A 2 / 3 , whereas the Z0 coupling is independent of A. Thus the former is the dominant source of NSD-PV for nuclei with A >= 20. We study NSD-PV effects using diatomic molecules, where signals are dramatically amplified by bringing rotational levels of opposite parity close to degeneracy in a strong magnetic field. Using a Stark-interference technique we measure the NSD-PV interaction matrix element. We present results that demonstrate statistical sensitivity to NSD-PV effects surpassing that of any previous atomic parity violation measurement, using the test system 138Ba19F. We also discuss investigations of systematics due to non-reversing stray E-fields, Enr together with B-field inhomogeneities, and short-term prospects for measuring the nuclear anapole moment of 137Ba. In the long term, our technique is sufficiently general and sensitive to enable measurements across a broad range of nuclei.

Magic angle spinning NMR with metallized rotors as cylindrical microwave resonators.

PubMed

Scott, Faith J; Sesti, Erika L; Choi, Eric J; Laut, Alexander J; Sirigiri, Jagadishwar R; Barnes, Alexander B

2018-04-19

We introduce a novel design for millimeter wave electromagnetic structures within magic angle spinning (MAS) rotors. In this demonstration, a copper coating is vacuum deposited onto the outside surface of a sapphire rotor at a thickness of 50 nm. This thickness is sufficient to reflect 197-GHz microwaves, yet not too thick as to interfere with radiofrequency fields at 300 MHz or prevent sample spinning due to eddy currents. Electromagnetic simulations of an idealized rotor geometry show a microwave quality factor of 148. MAS experiments with sample rotation frequencies of ω r /2π = 5.4 kHz demonstrate that the drag force due to eddy currents within the copper does not prevent sample spinning. Spectra of sodium acetate show resolved 13 C J-couplings of 60 Hz and no appreciable broadening between coated and uncoated sapphire rotors, demonstrating that the copper coating does not prevent shimming and high-resolution nuclear magnetic resonance spectroscopy. Additionally, 13 C Rabi nutation curves of ω 1 /2π = 103 kHz for both coated and uncoated rotors indicate no detrimental impact of the copper coating on radio frequency coupling of the nuclear spins to the sample coil. We present this metal coated rotor as a first step towards an MAS resonator. MAS resonators are expected to have a significant impact on developments in electron decoupling, pulsed dynamic nuclear polarization (DNP), room temperature DNP, DNP with low-power microwave sources, and electron paramagnetic resonance detection. Copyright © 2018 John Wiley & Sons, Ltd.

Optically induced cross relaxation via nitrogen-related defects for bulk diamond 13C hyperpolarization

NASA Astrophysics Data System (ADS)

Wunderlich, Ralf; Kohlrautz, Jonas; Abel, Bernd; Haase, Jürgen; Meijer, Jan

2017-12-01

In this Rapid Communication we utilize nuclear magnetic resonance to investigate the hyperpolarization effect of negatively charged nitrogen vacancy (NV) centers on bulk 13C nuclei in a diamond single crystal. We were able to identify several polarization peaks of a different sign at different magnetic fields in a region of some tens of Gauss centered around 50 mT . The bulk 13C hyperpolarization in the investigated field range is usually attributed to the excited state level anticrossing of the NV center. However, we found that this bulk hyperpolarization is caused by optically induced cross relaxation and that it takes place in the NV center ground state. The four-spin coupling between the polarized NV electron spin, the electron spin of a substitutional nitrogen impurity (P1), as well as its 14N nuclei and the 13C nuclear spin have to be considered. We introduce a simple theoretical model which completely fits with the experimental data and which clearly shows that the P1 centers are involved in the polarization process. We expect that the current work has a significant impact on future NV-based polarization applications.

Multidimensional High-Resolution Magic Angle Spinning and Solution-State NMR Characterization of 13C-labeled Plant Metabolites and Lignocellulose

PubMed Central

Mori, Tetsuya; Tsuboi, Yuuri; Ishida, Nobuhiro; Nishikubo, Nobuyuki; Demura, Taku; Kikuchi, Jun

2015-01-01

Lignocellulose, which includes mainly cellulose, hemicellulose, and lignin, is a potential resource for the production of chemicals and for other applications. For effective production of materials derived from biomass, it is important to characterize the metabolites and polymeric components of the biomass. Nuclear magnetic resonance (NMR) spectroscopy has been used to identify biomass components; however, the NMR spectra of metabolites and lignocellulose components are ambiguously assigned in many cases due to overlapping chemical shift peaks. Using our 13C-labeling technique in higher plants such as poplar samples, we demonstrated that overlapping peaks could be resolved by three-dimensional NMR experiments to more accurately assign chemical shifts compared with two-dimensional NMR measurements. Metabolites of the 13C-poplar were measured by high-resolution magic angle spinning NMR spectroscopy, which allows sample analysis without solvent extraction, while lignocellulose components of the 13C-poplar dissolved in dimethylsulfoxide/pyridine solvent were analyzed by solution-state NMR techniques. Using these methods, we were able to unambiguously assign chemical shifts of small and macromolecular components in 13C-poplar samples. Furthermore, using samples of less than 5 mg, we could differentiate between two kinds of genes that were overexpressed in poplar samples, which produced clearly modified plant cell wall components. PMID:26143886

Nuclear spin relaxation due to chemical shift anisotropy of gas-phase 129Xe.

PubMed

Hanni, Matti; Lantto, Perttu; Vaara, Juha

2011-08-14

Nuclear spin relaxation provides detailed dynamical information on molecular systems and materials. Here, first-principles modeling of the chemical shift anisotropy (CSA) relaxation time for the prototypic monoatomic (129)Xe gas is carried out, both complementing and predicting the results of NMR measurements. Our approach is based on molecular dynamics simulations combined with pre-parametrized ab initio binary nuclear shielding tensors, an "NMR force field". By using the Redfield relaxation formalism, the simulated CSA time correlation functions lead to spectral density functions that, for the first time, quantitatively determine the experimental spin-lattice relaxation times T(1). The quality requirements on both the Xe-Xe interaction potential and binary shielding tensor are investigated in the context of CSA T(1). Persistent dimers Xe(2) are found to be responsible for the CSA relaxation mechanism in the low-density limit of the gas, completely in line with the earlier experimental findings.

Quantum memory enhanced nuclear magnetic resonance of nanometer-scale samples with a single spin in diamond

NASA Astrophysics Data System (ADS)

Aslam, Nabeel; Pfender, Matthias; Zaiser, Sebastian; Favaro de Oliveira, Felipe; Momenzadeh, S. Ali; Denisenko, Andrej; Isoya, Junichi; Neumann, Philipp; Wrachtrup, Joerg

Recently nuclear magnetic resonance (NMR) of nanoscale samples at ambient conditions has been achieved with nitrogen-vacancy (NV) centers in diamond. So far the spectral resolution in the NV NMR experiments was limited by the sensor's coherence time, which in turn prohibited revealing the chemical composition and dynamics of the system under investigation. By entangling the NV electron spin sensor with a long-lived memory spin qubit we increase the spectral resolution of NMR measurement sequences for the detection of external nuclear spins. Applying the latter sensor-memory-couple it is particularly easy to track diffusion processes, to identify the molecules under study and to deduce the actual NV center depth inside the diamond. We performed nanoscale NMR on several liquid and solid samples exhibiting unique NMR response. Our method paves the way for nanoscale identification of molecule and protein structures and dynamics of conformational changes.

Spin coherent states phenomena probed by quantum state tomography in Zeeman perturbed nuclear quadrupole resonance

NASA Astrophysics Data System (ADS)

Teles, João; Auccaise, Ruben; Rivera-Ascona, Christian; Araujo-Ferreira, Arthur G.; Andreeta, José P.; Bonagamba, Tito J.

2018-07-01

Recently, we reported an experimental implementation of quantum information processing (QIP) by nuclear quadrupole resonance (NQR). In this work, we present the first quantum state tomography (QST) experimental implementation in the NQR QIP context. Two approaches are proposed, employing coherence selection by temporal and spatial averaging. Conditions for reduction in the number of cycling steps are analyzed, which can be helpful for larger spin systems. The QST method was applied to the study of spin coherent states, where the alignment-to-orientation phenomenon and the evolution of squeezed spin states show the effect of the nonlinear quadrupole interaction intrinsic to the NQR system. The quantum operations were implemented using a single-crystal sample of KClO3 and observing ^{35}Cl nuclei, which posses spin 3/2.

Sealing nuclear graphite with pyrolytic carbon

NASA Astrophysics Data System (ADS)

Feng, Shanglei; Xu, Li; Li, Li; Bai, Shuo; Yang, Xinmei; Zhou, Xingtai

2013-10-01

Pyrolytic carbon (PyC) coatings were deposited on IG-110 nuclear graphite by thermal decomposition of methane at ∼1830 °C. The PyC coatings are anisotropic and airtight enough to protect IG-110 nuclear graphite against the permeation of molten fluoride salts and the diffusion of gases. The investigations indicate that the sealing nuclear graphite with PyC coating is a promising method for its application in Molten Salt Reactor (MSR).

Spin-polarized electron current from carbon-doped open armchair boron nitride nanotubes: Implication for nano-spintronic devices

NASA Astrophysics Data System (ADS)

Zhou, Gang; Duan, Wenhui

2007-03-01

Spin-polarized density functional calculations show that the substitutional doping of carbon (C) atom at the mouth changes the atomic and spin configurations of open armchair boron nitride nanotubes (BNNTs). The occupied/unoccupied deep gap states are observed with the significant spin-splitting. The structures and spin-polarized properties are basically stable under the considerable electric field, which is important for practical applications. The magnetization mechanism is attributed to the interactions of s, p states between the C and its neighboring B or N atoms. Ultimately, advantageous geometrical and electronic effects mean that C-doped open armchair BNNTs would have promising applications in nano-spintronic devices.

A Molecular Budget for a Peatland Based Upon 13C Solid-State Nuclear Magnetic Resonance

NASA Astrophysics Data System (ADS)

Moody, Catherine S.; Worrall, Fred; Clay, Gareth D.; Burt, Tim P.; Apperley, David C.; Rose, Rob

2018-02-01

Peatlands can accumulate organic matter into long-term carbon (C) storage within the soil profile. This study used solid-state 13C nuclear magnetic resonance (13C-NMR) to investigate the transit of organic C through a peatland ecosystem to understand the molecular budget that accompanies the long-term accumulation of C. Samples of biomass, litter, peat soil profile, particulate organic matter, and dissolved organic matter (DOM) were taken from the Moor House National Nature Reserve, a peat-covered catchment in northern England where both the dry matter and C budget for the ecosystem were known. The results showed that: The interpretation of the 13C-NMR spectra shows that polysaccharides are preferentially removed through the ecosystem, while lignin components are preferentially retained and come to dominate the organic matter accumulated at depth in the profile. The DOM is derived from the oxidation of both biomass and the degradation of lignin, while the particulate organic matter is derived from erosion of the peat profile. The DOM is differentiated by its proportion of oxidized functional groups and not by its aromatic content. The changes in functionality leading to DOM production suggest side chain oxidation resulting in C-C cleavage/depolymerisation of lignin, a common reaction within white rot fungi. The 13C-NMR budget shows that O-alkyl functional groups are disproportionately lost between primary production and accumulation in the deep peat, while C-alkyl functional groups are disproportionately preserved. The carbon lost as gases (CO2 and CH4) was estimated to be composed of 93% polysaccharide-derived carbon and 7% lignin-derived carbon.

Elucidation of metabolic pathways in glycogen-accumulating organisms with in vivo 13C nuclear magnetic resonance.

PubMed

Lemos, Paulo C; Dai, Yu; Yuan, Zhiguo; Keller, Jurg; Santos, Helena; Reis, Maria A M

2007-11-01

Glycogen-accumulating organisms (GAOs) are found in enhanced biological phosphorus removal systems where they compete with polyphosphate-accumulating organisms for external carbon substrates. (13)C nuclear magnetic resonance ((13)C-NMR) was used to elucidate the metabolic pathways operating in an enriched GAO culture dominated by two known GAOs (81.2%). The experiments consisted of adding (13)C-acetate (labelled on position 1 or 2) to the culture under anaerobic conditions, and operating the culture through a cycle consisting of an anaerobic, an aerobic and a further anaerobic phase. The carbon transformations over the cycle were monitored using in vivo(13)C-NMR. The two-carbon moieties in hydroxybutyrate and hydroxyvalerate were derived from acetate, while the propionyl precursor of hydroxyvalerate was primarily derived from glycogen, with only a small fraction originating from acetate. Comparison of the labelling patterns in hydroxyvalerate at the end of the first and the second anaerobic periods in pulse experiments with 2-(13)C-acetate showed that the Entner-Doudoroff (ED) pathway was used for the breakdown of glycogen. This conclusion was further supported by the labelling pattern on glycogen observed in the pulse experiments with 1-(13)C-acetate, which can only be explained by the operation of ED with recycling of pyruvate and glyceraldehyde 3-phosphate via gluconeogenesis. The activity of the ED pathway for glycogen degradation by GAOs is demonstrated here for the first time. In addition, the decarboxylating part of the tricarboxylic acid cycle was confirmed to operate also under anaerobic conditions.

Nuclear-driven electron spin rotations in a coupled silicon quantum dot and single donor system

NASA Astrophysics Data System (ADS)

Harvey-Collard, Patrick; Jacobson, Noah Tobias; Rudolph, Martin; Ten Eyck, Gregory A.; Wendt, Joel R.; Pluym, Tammy; Lilly, Michael P.; Pioro-Ladrière, Michel; Carroll, Malcolm S.

Single donors in silicon are very good qubits. However, a central challenge is to couple them to one another. To achieve this, many proposals rely on using a nearby quantum dot (QD) to mediate an interaction. In this work, we demonstrate the coherent coupling of electron spins between a single 31P donor and an enriched 28Si metal-oxide-semiconductor few-electron QD. We show that the electron-nuclear spin interaction can drive coherent rotations between singlet and triplet electron spin states. Moreover, we are able to tune electrically the exchange interaction between the QD and donor electrons. The combination of single-nucleus-driven rotations and voltage-tunable exchange provides all elements for future all-electrical control of a spin qubit, and requires only a single dot and no additional magnetic field gradients. This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

Study on thick film spin-on carbon hardmask

NASA Astrophysics Data System (ADS)

Kim, Taeho; Kim, Youngmin; Hwang, Sunmin; Lee, Hyunsoo; Han, Miyeon; Lim, Sanghak

2017-03-01

A thick spin-on carbon hardmask (SOH) material is designed to overcome inherent problems of amorphous deposited carbon layer (ACL) and thick photoresist. For ACL in use of semiconductor production process, especially when film thickness from sub-micrometer up to few micrometers is required, not only its inherent low transparency at long wavelength light often causes alignment problems with under layers, but also considerable variation of film thickness within a wafer can also cause patterning problems. To avoid these issues, a thick SOH is designed with monomers of high transparency and good solubility at the same time. In comparison with photoresist, the SOH has good etch resistance and high thermal stability, and it provides wide process window of decreased film thickness and increased thermal budget up to 400°C after processes such as high temperature deposition of SiON. In order to achieve high thickness along with uniform film, many solvent factors was considered such as solubility parameter, surface tension, vapor pressure, and others. By optimizing many solvent factors, we were able to develop a product with a good coating performance

EPR spin probe and spin label studies of some low molecular and polymer micelles

NASA Astrophysics Data System (ADS)

Wasserman, A. M.; Kasaikin, V. A.; Timofeev, V. P.

1998-12-01

The rotational mobility of spin probes of different shape and size in low molecular and polymer micelles has been studied. Several probes having nitroxide fragment localized either in the vicinity of micelle interface or in the hydrocarbon core have been used. Upon increasing the number of carbon atoms in hydrocarbon chain of detergent from 7 to 13 (sodium alkyl sulfate micelles) or from 12 to 16 (alkyltrimethylammonium bromide micelles) the rotational mobility of spin probes is decreased by the factor 1.5-2.0. The spin probe rotational mobility in polymer micelles (the complexes of alkyltrimethylammonium bromides and polymethacrylic or polyacrylic acids) is less than mobility in free micelles of the same surfactants. The study of EPR-spectra of spin labeled polymethacrylic acid (PMA) indicated that formation of water soluble complexes of polymer and alkyltrimethylammonium bromides in alkaline solutions (pH 9) does not affect the polymer segmental mobility. On the other hand, the polymer complexes formation in slightly acidic water solution (pH 6) breaks down the compact PMA conformation, thus increasing the polymer segmental mobility. Possible structures of polymer micelles are discussed.

Synthesis of carbon-11, fluorine-18, and nitrogen-13 labeled radiotracers for biomedical applications. Nuclear Science Series: Nuclear Medicine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fowler, J.S.; Wolf, A.P.

1982-09-01

Carbon 11, Fluorine 18, and Nitrogen 13-labeled radiotracers are reviewed from the standpoint of synthetic organic chemistry while keeping in perspective the necessity of integrating the organic chemistry with the design and ultimate application of the radiotracer. The reactions used, the principles used to adapt these reactions to labeling with short-lived radionuclides, and the concepts of chemical reactivity form the framework upon which synthetic strategies for short-lived radiotracers are developed. Potentially new routes are suggested which may be applied to problems in labeling organic molecules. (ACR)

Efficient Synthesis of Molecular Precursors for Para-Hydrogen-Induced Polarization of Ethyl Acetate-1-(13) C and Beyond.

PubMed

Shchepin, Roman V; Barskiy, Danila A; Coffey, Aaron M; Manzanera Esteve, Isaac V; Chekmenev, Eduard Y

2016-05-10

A scalable and versatile methodology for production of vinylated carboxylic compounds with (13) C isotopic label in C1 position is described. It allowed synthesis of vinyl acetate-1-(13) C, which is a precursor for preparation of (13) C hyperpolarized ethyl acetate-1-(13) C, which provides a convenient vehicle for potential in vivo delivery of hyperpolarized acetate to probe metabolism in living organisms. Kinetics of vinyl acetate molecular hydrogenation and polarization transfer from para-hydrogen to (13) C via magnetic field cycling were investigated. Nascent proton nuclear spin polarization (%PH ) of ca. 3.3 % and carbon-13 polarization (%P13C ) of ca. 1.8 % were achieved in ethyl acetate utilizing 50 % para-hydrogen corresponding to ca. 50 % polarization transfer efficiency. The use of nearly 100% para-hydrogen and the improvements of %PH of para-hydrogen-nascent protons may enable production of (13) C hyperpolarized contrast agents with %P13C of 20-50 % in seconds using this chemistry. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coupling XRD, EXAFS, and 13C NMR to study the effect of the carbon stoichiometry on the local structure of UC(1±x).

PubMed

Carvajal Nuñez, U; Martel, L; Prieur, D; Lopez Honorato, E; Eloirdi, R; Farnan, I; Vitova, T; Somers, J

2013-10-07

A series of uranium carbide samples, prepared by arc melting with a C/U ratio ranging from 0.96 to 1.04, has been studied by X-ray diffraction (XRD), (13)C nuclear magnetic resonance (NMR), and extended X-ray absorption fine structure (EXAFS). XRD determines phase uniqueness and the increase of the lattice parameter versus the carbon content. In contrast, (13)C NMR detects the different carbon environments in the lattice and in this study, clearly identifies the presence of discrete peaks for carbon in the octahedral lattice site in UC and an additional peak associated with excess carbon in hyperstoichiometric samples. Two peaks associated with different levels of carbon deficiency are detected for all hypostoichiometric compositions. More than one carbon environment is always detected by (13)C NMR. This exemplifies the difficulty in obtaining a perfect stoichiometric uranium monocarbide UC(1.00). The (13)C MAS spectra of uranium carbides exhibit the effects resulting from the carbon content on both the broadening of the peaks and on the Knight shift. An abrupt spectral change occurs between hypo- and hyperstoichiometric samples. The results obtained by EXAFS highlight subtle differences between the different stoichiometries, and in the hyperstoichiometric samples, the EXAFS results are consistent with the excess carbon atoms being in the tetrahedral interstitial position.

Abnormal Elasticity of Single-Crystal Magnesiosiderite across the Spin Transition in Earth's Lower Mantle

NASA Astrophysics Data System (ADS)

Fu, S.; Yang, J.; Lin, J. F.

2016-12-01

Carbon can be transported into deep Earth's interior via subduction of carbonated oceanic crust, hosted as Mg-Fe bearing carbonates. The existence of stable carbonate can significantly affect our understanding on geochemical and geophysical properties of the planet. Early studies have shown that iron spin-pairing transition could occur in the iron-enriched carbonates, generally called magnesiosiderite, under lower mantle conditions. The pressure-induced spin state change is accompanied by a sudden volume collaps. However, the effects of the spin-pairing transition on single-crystal elasticity of magnesiosiderite under high pressure conditions are still unclear. Understanding the elasticity of single-crystal magnesiosiderite at relevant lower mantle conditions plays an important role in better understanding the seismic signatures in the carbon-enriched region, and to constrain carbon storage and recycling in the mantle. In order to solve all individual elastic constants (C11, C22, C33, C44, C55, C66, C12, C23, and C13) of magnesiosiderite at high pressures via Christoffel's equations, we employed Brillouin Light Scattering (BLS) to measure shear wave (Vs) and compressional wave velocities (Vp) as a function of the azimuthal angle under lower mantle pressures, accompanied by Impulsive Stimulate Light Scattering (ISS) to measure the Vp when pressures are too high to measure it by BLS. A general thermoelastic modelling was developed to fit the elastic softening within the spin transition. We will further discuss the effects of pressures, as well as iron spin states, on the single-crystal elasticity and seismic parameters (Vp and Vs anisotropy AVp, AVs, etc) at lower mantle conditions. These results could provide clues in explaining regional seismic heterogeneities in deep mantle.

Lithium dynamics in carbon-rich polymer-derived SiCN ceramics probed by nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Baek, Seung-Ho; Reinold, Lukas Mirko; Graczyk-Zajac, Magdalena; Riedel, Ralf; Hammerath, Franziska; Büchner, Bernd; Grafe, Hans-Joachim

2014-05-01

We report 7Li, 29Si, and 13C NMR studies of two different carbon-rich SiCN ceramics SiCN-1 and SiCN-3 derived from the preceramic polymers polyphenylvinylsilylcarbodiimide and polyphenylvinylsilazane, respectively. From the spectral analysis of the three nuclei, we find that only the 13C spectrum is strongly influenced by Li insertion/extraction, suggesting that carbon phases are the major electrochemically active sites for Li storage. Temperature (T) and Larmor frequency (ωL) dependences of the 7Li linewidth and spin-lattice relaxation rates T1-1 are described by an activated law with the activation energy EA of 0.31 eV and the correlation time τ0 in the high temperature limit of 1.3 ps. The 3 / 2 power law dependence of T1-1 on ωL which deviates from the standard Bloembergen, Purcell, and Pound (BPP) model implies that the Li motion on the μs timescale is governed by continuum diffusion mechanism rather than jump diffusion. On the other hand, the rotating frame relaxation rate T1ρ-1 results suggest that the slow motion of Li on the ms timescale may be affected by complex diffusion and/or non-diffusion processes.

Fully gapped spin-singlet superconductivity in noncentrosymmetric PbTaSe2: 207Pb nuclear magnetic resonance study

NASA Astrophysics Data System (ADS)

Maeda, S.; Matano, K.; Zheng, Guo-qing

2018-05-01

We report the 207Pb nuclear magnetic resonance (NMR) measurements on polycrystalline sample of PbTaSe2 with noncentrosymmetric crystal structure and topological electronic band. The nuclear spin-lattice relaxation rate 1 /T1 shows a suppressed coherence peak below the superconducting transition temperature Tc=4.05 K and decreases as an exponential function of temperature. The penetration depth derived from the NMR spectrum is almost temperature independent below T =0.7 Tc. The Knight shift K decreases below Tc. These results suggest spin-singlet superconductivity with a fully opened gap 2 Δ =3.5 kBTc in PbTaSe2.

Efficient calculation of nuclear spin-rotation constants from auxiliary density functional theory.

PubMed

Zuniga-Gutierrez, Bernardo; Camacho-Gonzalez, Monica; Bendana-Castillo, Alfonso; Simon-Bastida, Patricia; Calaminici, Patrizia; Köster, Andreas M

2015-09-14

The computation of the spin-rotation tensor within the framework of auxiliary density functional theory (ADFT) in combination with the gauge including atomic orbital (GIAO) scheme, to treat the gauge origin problem, is presented. For the spin-rotation tensor, the calculation of the magnetic shielding tensor represents the most demanding computational task. Employing the ADFT-GIAO methodology, the central processing unit time for the magnetic shielding tensor calculation can be dramatically reduced. In this work, the quality of spin-rotation constants obtained with the ADFT-GIAO methodology is compared with available experimental data as well as with other theoretical results at the Hartree-Fock and coupled-cluster level of theory. It is found that the agreement between the ADFT-GIAO results and the experiment is good and very similar to the ones obtained by the coupled-cluster single-doubles-perturbative triples-GIAO methodology. With the improved computational performance achieved, the computation of the spin-rotation tensors of large systems or along Born-Oppenheimer molecular dynamics trajectories becomes feasible in reasonable times. Three models of carbon fullerenes containing hundreds of atoms and thousands of basis functions are used for benchmarking the performance. Furthermore, a theoretical study of temperature effects on the structure and spin-rotation tensor of the H(12)C-(12)CH-DF complex is presented. Here, the temperature dependency of the spin-rotation tensor of the fluorine nucleus can be used to identify experimentally the so far unknown bent isomer of this complex. To the best of our knowledge this is the first time that temperature effects on the spin-rotation tensor are investigated.

Magnetic equivalence of terminal nuclei in the azide anion broken by nuclear spin relaxation

NASA Astrophysics Data System (ADS)

Bernatowicz, P.; Szymański, S.

NMR spectra of water solution of sodium azide selectively 15N labelled in the central position were studied using an iterative least-squares method. In agreement with predictions based on Bloch-Wangsness-Redfield nuclear spin relaxation theory, it is demonstrated that quadrupolar relaxation of the magnetically equivalent terminal 14N (spin-1) nuclei in the azide anion renders the J coupling between these nuclei an observable quantity. In isotropic fluids, this seems to be the first experimental evidence of relaxation-broken magnetic equivalence symmetry.

Production of carbon-13-labeled cadaverine by engineered Corynebacterium glutamicum using carbon-13-labeled methanol as co-substrate.

PubMed

Leßmeier, Lennart; Pfeifenschneider, Johannes; Carnicer, Marc; Heux, Stephanie; Portais, Jean-Charles; Wendisch, Volker F

2015-12-01

Methanol, a one-carbon compound, can be utilized by a variety of bacteria and other organisms as carbon and energy source and is regarded as a promising substrate for biotechnological production. In this study, a strain of non-methylotrophic Corynebacterium glutamicum, which was able to produce the polyamide building block cadaverine as non-native product, was engineered for co-utilization of methanol. Expression of the gene encoding NAD+-dependent methanol dehydrogenase (Mdh) from the natural methylotroph Bacillus methanolicus increased methanol oxidation. Deletion of the endogenous aldehyde dehydrogenase genes ald and fadH prevented methanol oxidation to carbon dioxide and formaldehyde detoxification via the linear formaldehyde dissimilation pathway. Heterologous expression of genes for the key enzymes hexulose-6-phosphate synthase and 6-phospho-3-hexuloisomerase of the ribulose monophosphate (RuMP) pathway in this strain restored growth in the presence of methanol or formaldehyde, which suggested efficient formaldehyde detoxification involving RuMP key enzymes. While growth with methanol as sole carbon source was not observed, the fate of 13C-methanol added as co-substrate to sugars was followed and the isotopologue distribution indicated incorporation into central metabolites and in vivo activity of the RuMP pathway. In addition, 13C-label from methanol was traced to the secreted product cadaverine. Thus, this synthetic biology approach led to a C. glutamicum strain that converted the non-natural carbon substrate methanol at least partially to the non-native product cadaverine.

Four-Component Relativistic Density-Functional Theory Calculations of Nuclear Spin-Rotation Constants: Relativistic Effects in p-Block Hydrides.

PubMed

Komorovsky, Stanislav; Repisky, Michal; Malkin, Elena; Demissie, Taye B; Ruud, Kenneth

2015-08-11

We present an implementation of the nuclear spin-rotation (SR) constants based on the relativistic four-component Dirac-Coulomb Hamiltonian. This formalism has been implemented in the framework of the Hartree-Fock and Kohn-Sham theory, allowing assessment of both pure and hybrid exchange-correlation functionals. In the density-functional theory (DFT) implementation of the response equations, a noncollinear generalized gradient approximation (GGA) has been used. The present approach enforces a restricted kinetic balance condition for the small-component basis at the integral level, leading to very efficient calculations of the property. We apply the methodology to study relativistic effects on the spin-rotation constants by performing calculations on XHn (n = 1-4) for all elements X in the p-block of the periodic table and comparing the effects of relativity on the nuclear SR tensors to that observed for the nuclear magnetic shielding tensors. Correlation effects as described by the density-functional theory are shown to be significant for the spin-rotation constants, whereas the differences between the use of GGA and hybrid density functionals are much smaller. Our calculated relativistic spin-rotation constants at the DFT level of theory are only in fair agreement with available experimental data. It is shown that the scaling of the relativistic effects for the spin-rotation constants (varying between Z(3.8) and Z(4.5)) is as strong as for the chemical shieldings but with a much smaller prefactor.

Carbon flux analysis by 13C nuclear magnetic resonance to determine the effect of CO2 on anaerobic succinate production by Corynebacterium glutamicum.

PubMed

Radoš, Dušica; Turner, David L; Fonseca, Luís L; Carvalho, Ana Lúcia; Blombach, Bastian; Eikmanns, Bernhard J; Neves, Ana Rute; Santos, Helena

2014-05-01

Wild-type Corynebacterium glutamicum produces a mixture of lactic, succinic, and acetic acids from glucose under oxygen deprivation. We investigated the effect of CO2 on the production of organic acids in a two-stage process: cells were grown aerobically in glucose, and subsequently, organic acid production by nongrowing cells was studied under anaerobic conditions. The presence of CO2 caused up to a 3-fold increase in the succinate yield (1 mol per mol of glucose) and about 2-fold increase in acetate, both at the expense of l-lactate production; moreover, dihydroxyacetone formation was abolished. The redistribution of carbon fluxes in response to CO2 was estimated by using (13)C-labeled glucose and (13)C nuclear magnetic resonance (NMR) analysis of the labeling patterns in end products. The flux analysis showed that 97% of succinate was produced via the reductive part of the tricarboxylic acid cycle, with the low activity of the oxidative branch being sufficient to provide the reducing equivalents needed for the redox balance. The flux via the pentose phosphate pathway was low (~5%) regardless of the presence or absence of CO2. Moreover, there was significant channeling of carbon to storage compounds (glycogen and trehalose) and concomitant catabolism of these reserves. The intracellular and extracellular pools of lactate and succinate were measured by in vivo NMR, and the stoichiometry (H(+):organic acid) of the respective exporters was calculated. This study shows that it is feasible to take advantage of natural cellular regulation mechanisms to obtain high yields of succinate with C. glutamicum without genetic manipulation.

Self-diffusion of electrolyte species in model battery electrodes using Magic Angle Spinning and Pulsed Field Gradient Nuclear Magnetic Resonance

NASA Astrophysics Data System (ADS)

Tambio, Sacris Jeru; Deschamps, Michaël; Sarou-Kanian, Vincent; Etiemble, Aurélien; Douillard, Thierry; Maire, Eric; Lestriez, Bernard

2017-09-01

Lithium-ion batteries are electrochemical storage devices using the electrochemical activity of the lithium ion in relation to intercalation compounds owing to mass transport phenomena through diffusion. Diffusion of the lithium ion in the electrode pores has been poorly understood due to the lack of experimental techniques for measuring its self-diffusion coefficient in porous media. Magic-Angle Spinning, Pulsed Field Gradient, Stimulated-Echo Nuclear Magnetic Resonance (MAS-PFG-STE NMR) was used here for the first time to measure the self-diffusion coefficients of the electrolyte species in the LP30 battery electrolyte (i.e. a 1 M solution of LiPF6 dissolved in 1:1 Ethylene Carbonate - Dimethyl Carbonate) in model composites. These composite electrodes were made of alumina, carbon black and PVdF-HFP. Alumina's magnetic susceptibility is close to the measured magnetic susceptibility of the LP30 electrolyte thereby limiting undesirable internal field gradients. Interestingly, the self-diffusion coefficient of lithium ions decreases with increasing carbon content. FIB-SEM was used to describe the 3D geometry of the samples. The comparison between the reduction of self-diffusion coefficients as measured by PFG-NMR and as geometrically derived from FIB/SEM tortuosity values highlights the contribution of specific interactions at the material/electrolyte interface on the lithium transport properties.

Herpes simplex virus 2 UL13 protein kinase disrupts nuclear lamins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cano-Monreal, Gina L.; Wylie, Kristine M.; Cao, Feng

2009-09-15

Herpesviruses must cross the inner nuclear membrane and underlying lamina to exit the nucleus. HSV-1 US3 and PKC can phosphorylate lamins and induce their dispersion but do not elicit all of the phosphorylated lamin species produced during infection. UL13 is a serine threonine protein kinase conserved among many herpesviruses. HSV-1 UL13 phosphorylates US3 and thereby controls UL31 and UL34 nuclear rim localization, indicating a role in nuclear egress. Here, we report that HSV-2 UL13 alone induced conformational changes in lamins A and C and redistributed lamin B1 from the nuclear rim to intranuclear granular structures. HSV-2 UL13 directly phosphorylated laminsmore » A, C, and B1 in vitro, and the lamin A1 tail domain. HSV-2 infection recapitulated the lamin alterations seen upon expression of UL13 alone, and other alterations were also observed, indicating that additional viral and/or cellular proteins cooperate with UL13 to alter lamins during HSV-2 infection to allow nuclear egress.« less

Nuclear Spin Dependent Parity Violation in Diatomic Molecules

NASA Astrophysics Data System (ADS)

Altuntas, Emine; Cahn, Sidney; Demille, David; Kozlov, Mikhail

2016-05-01

Nuclear spin-dependent parity violation (NSD-PV) effects arise from exchange of the Z0 boson between electrons and the nucleus, and from interaction of electrons with the nuclear anapole moment, a parity-odd magnetic moment. The latter scales with nucleon number of the nucleus A as A 2 / 3 , whereas the Z0 coupling is independent of A. Thus the former is the dominant source of NSD-PV for nuclei with A >= 20. We study NSD-PV effects using diatomic molecules, where signals are dramatically amplified by bringing rotational levels of opposite parity close to degeneracy in a strong magnetic field. The NSD-PV interaction matrix element is measured using a Stark-interference technique. We present results that demonstrate statistical sensitivity to NSD-PV effects surpassing that of any previous atomic parity violation measurement, using the test system 138 Ba19 F. We report our progress on measuring and cancelling systematic effects due to combination of non-reversing stray E-fields, Enr with B-field inhomogeneities. Short-term prospects for measuring the nuclear anapole moment of 137 Ba19 F are discussed. In the long term, our technique is sufficiently general and sensitive to enable measurements across a broad range of nuclei.

Nuclear Spin Dependent Parity Violation in Diatomic Molecules

NASA Astrophysics Data System (ADS)

Altuntas, Emine; Cahn, Sidney; Demille, David

2016-09-01

Nuclear spin-dependent parity violation (NSD-PV) effects arise from exchange of the Z0 boson between electrons and the nucleus, and from interaction of electrons with the nuclear anapole moment, a parity-odd magnetic moment. The latter scales with nucleon number of the nucleus A as A2/3 , whereas the Z0 coupling is independent of A. Thus the former is the dominant source of NSD-PV for nuclei with A >= 20 . We study NSD-PV effects using diatomic molecules, where signals are dramatically amplified by bringing rotational levels of opposite parity close to degeneracy in a strong magnetic field. The NSD-PV interaction matrix element is measured using a Stark-interference technique. We present results that demonstrate statistical sensitivity to NSD-PV effects surpassing that of any previous atomic parity violation measurement, using the test system 138Ba19F. We report our progress on measuring and cancelling systematic effects due to combination of non-reversing stray E-fields, Enr with B-field inhomogeneities. Short-term prospects for measuring the nuclear anapole moment of 137Ba19F are discussed. In the long term, our technique is sufficiently general and sensitive to enable measurements across a broad range of nuclei.

Squeezed spin states: Squeezing the spin uncertainty relations

NASA Technical Reports Server (NTRS)

Kitagawa, Masahiro; Ueda, Masahito

1993-01-01

The notion of squeezing in spin systems is clarified, and the principle for spin squeezing is shown. Two twisting schemes are proposed as building blocks for spin squeezing and are shown to reduce the standard quantum noise, s/2, of the coherent S-spin state down to the order of S(sup 1/3) and 1/2. Applications to partition noise suppression are briefly discussed.

One-electron versus electron-electron interaction contributions to the spin-spin coupling mechanism in nuclear magnetic resonance spectroscopy: Analysis of basic electronic effects

NASA Astrophysics Data System (ADS)

Gräfenstein, Jürgen; Cremer, Dieter

2004-12-01

For the first time, the nuclear magnetic resonance (NMR) spin-spin coupling mechanism is decomposed into one-electron and electron-electron interaction contributions to demonstrate that spin-information transport between different orbitals is not exclusively an electron-exchange phenomenon. This is done using coupled perturbed density-functional theory in conjunction with the recently developed J-OC-PSP [=J-OC-OC-PSP: Decomposition of J into orbital contributions using orbital currents and partial spin polarization)] method. One-orbital contributions comprise Ramsey response and self-exchange effects and the two-orbital contributions describe first-order delocalization and steric exchange. The two-orbital effects can be characterized as external orbital, echo, and spin transport contributions. A relationship of these electronic effects to zeroth-order orbital theory is demonstrated and their sign and magnitude predicted using simple models and graphical representations of first order orbitals. In the case of methane the two NMR spin-spin coupling constants result from totally different Fermi contact coupling mechanisms. 1J(C,H) is the result of the Ramsey response and the self-exchange of the bond orbital diminished by external first-order delocalization external one-orbital effects whereas 2J(H,H) spin-spin coupling is almost exclusively mitigated by a two-orbital steric exchange effect. From this analysis, a series of prediction can be made how geometrical deformations, electron lone pairs, and substituent effects lead to a change in the values of 1J(C,H) and 2J(H,H), respectively, for hydrocarbons.

Carbon 13 exchanges between the atmosphere and biosphere

NASA Astrophysics Data System (ADS)

Fung, I.; Field, C. B.; Berry, J. A.; Thompson, M. V.; Randerson, J. T.; MalmströM, C. M.; Vitousek, P. M.; Collatz, G. James; Sellers, P. J.; Randall, D. A.; Denning, A. S.; Badeck, F.; John, J.

1997-12-01

We present a detailed investigation of the gross 12C and 13C exchanges between the atmosphere and biosphere and their influence on the δ13C variations in the atmosphere. The photosynthetic discrimination Δ against 13C is derived from a biophysical model coupled to a general circulation model [Sellers et al., 1996a], where stomatal conductance and carbon assimilation are determined simultaneously with the ambient climate. The δ13C of the respired carbon is calculated by a biogeochemical model [Potter et al., 1993; Randerson et al., 1996] as the sum of the contributions from compartments with varying ages. The global flux-weighted mean photosynthetic discrimination is 12-16‰, which is lower than previous estimates. Factors that lower the discrimination are reduced stomatal conductance and C4 photosynthesis. The decreasing atmospheric δ13C causes an isotopic disequilibrium between the outgoing and incoming fluxes; the disequilibrium is ˜0.33‰ for 1988. The disequilibrium is higher than previous estimates because it accounts for the lifetime of trees and for the ages rather than turnover times of the biospheric pools. The atmospheric δ13C signature resulting from the biospheric fluxes is investigated using a three-dimensional atmospheric tracer model. The isotopic disequilibrium alone produces a hemispheric difference of ˜0.02‰ in atmospheric δ13C, comparable to the signal from a hypothetical carbon sink of 0.5 Gt C yr-1 into the midlatitude northern hemisphere biosphere. However, the rectifier effect, due to the seasonal covariation of CO2 fluxes and height of the atmospheric boundary layer, yields a background δ13C gradient of the opposite sign. These effects nearly cancel thus favoring a stronger net biospheric uptake than without the background CO2 gradient. Our analysis of the globally averaged carbon budget for the decade of the 1980s indicates that the biospheric uptake of fossil fuel CO2 is likely to be greater than the oceanic uptake; the

Controls on the Origin and Cycling of Riverine Dissolved Inorganic Carbon in the Brazos River, Texas

NASA Astrophysics Data System (ADS)

Zeng, F.; Masiello, C. A.; Hockaday, W. C.

2008-12-01

Rivers are generally supersaturated in CO2 with respect to the atmosphere. However, there is little agreement on the sources and turnover times of excess CO2 in river waters. This is likely due to varying dominant controls on carbon sources (e.g. geologic setting, climate, land use, or human activities). In this study, we measured carbon isotopic signatures (δ13C and Δ14C) of riverine dissolved inorganic carbon (DIC), as well as solid state cross polarization/magic angle spinning (CP/MAS) 13C nuclear magnetic resonance (NMR) of particulate organic carbon (POC), to determine carbon sources fuelling respiration of the Brazos River in Texas. We found that sources of riverine CO2 varied significantly along the length of the Brazos. In the middle Brazos (between Graham and Waco), which is partially underlain by limestone, riverine DIC had average Δ14C of 74 ‰ and δ13C of -7.5 ‰, suggesting that riverine CO2 is derived almost entirely from contemporary carbon (less than 5 years old) with little evidence of carbonate input, probably due to the damming upstream of Waco. In the lower Brazos (downstream of Bryan), riverine DIC was highly depleted in 14C (average Δ14C = -148.5 ‰) and enriched in 13C (average δ13C= -9.32 ‰), indicative of the presence of old carbonate. Since there is no carbonate bedrock in contact with the river in this area, the most likely source of old carbonate is the shell used in road and building construction throughout the 19th century. Our results suggest that the effect of human activities superimposes and even surpasses the effect of natural controls (e.g. geologic setting and climate) on C cycling in the Brazos.

Basis for calculating cross sections for nuclear magnetic resonance spin-modulated polarized neutron scattering.

PubMed

Kotlarchyk, Michael; Thurston, George M

2016-12-28

In this work we study the potential for utilizing the scattering of polarized neutrons from nuclei whose spin has been modulated using nuclear magnetic resonance (NMR). From first principles, we present an in-depth development of the differential scattering cross sections that would arise in such measurements from a hypothetical target system containing nuclei with non-zero spins. In particular, we investigate the modulation of the polarized scattering cross sections following the application of radio frequency pulses that impart initial transverse rotations to selected sets of spin-1/2 nuclei. The long-term aim is to provide a foundational treatment of the scattering cross section associated with enhancing scattering signals from selected nuclei using NMR techniques, thus employing minimal chemical or isotopic alterations, so as to advance the knowledge of macromolecular or liquid structure.

Controlling Spin Coherence with Semiconductor Nanostructures

NASA Astrophysics Data System (ADS)

Awschalom, David D.

We present two emerging opportunities for manipulating and communicating coherent spin states in semiconductors. First, we show that semiconductor microcavities offer unique means of controlling light-matter interactions in confined geometries, resulting in a wide range of applications in optical communications and inspiring proposals for quantum information processing and computational schemes. Studies of spin dynamics in microcavities — a new and promising research field — have revealed novel effects such as polarization beats, stimulated spin scattering, and giant Faraday rotation. Here, we study the electron spin dynamics in optically-pumped GaAs microdisk lasers with quantum wells and interface-fluctuation quantum dots in the active region. In particular, we examine how the electron spin dynamics are modified by the stimulated emission in the disks, and observe an enhancement of the spin coherence time when the optical excitation is in resonance with a high quality (Q ~ 5000) lasing mode.1 This resonant enhancement, contrary to expectations from the observed trend in the carrier recombination time, is then manipulated by altering the cavity design and dimensions. In analogy to devices based on excitonic coherence, this ability to engineer coherent interactions between electron spins and photons may provide novel pathways towards spin dependent quantum optoelectronics. In a second example, the nitrogen-vacancy (N-V) center in diamond has garnered interest as a room-temperature solid-state system not only for exploring electronic and nuclear spin phenomena but also as a candidate for spin-based quantum information processing. Spin coherence times of up to 50 microseconds have been reported for ensembles of N-V centers and a two-qubit gate utilizing the electron spin of a N-V center and the nuclear spin of a nearby C-13 atom has been demonstrated. Here, we present experiments using angle-resolved magneto-photoluminescence microscopy to investigate anisotropic

C-13 nuclear magnetic resonance in organic geochemistry.

NASA Technical Reports Server (NTRS)

Balogh, B.; Wilson, D. M.; Burlingame, A. L.

1972-01-01

Study of C-13 nuclear magnetic resonance (NMR) spectra of polycyclic fused systems. The fingerprint qualities of the natural abundance in C-13 NMR spectra permitting unequivocal identification of these compounds is discussed. The principle of structural additivity of C-13 NMR information is exemplified on alpha and beta androstanes, alpha and beta cholestanes, ergostanes, sitostanes, and isodecanes.

13C chemical-shift anisotropy of alkyl-substituted aromatic carbon in anthracene derivatives.

PubMed

Hoop, Cody L; Iuliucci, Robbie J

2013-06-01

The (13)C chemical-shift anisotropy in anthracene derivatives (9,10-dimethylanthracene, 9,10-dihydroanthracene, dianthracene, and triptycene) has been measured by the 2D FIREMAT timed pulse sequence and the corresponding set of principal values has been determined by the TIGER processing method. These molecules expand the data base of (13)C CSA measurements of fused aromatic rings some bridged by sp(3) carbon resulting in an unusual bonding configuration, which leads to distinctive aromatic (13)C CSA values. Crystal lattice distortions to the CSA were observed to change the isotropic shift by 2.5 to 3.3 ppm and changes as large as 8.3 ppm in principal components. Modeling of the CSA data by GIPAW DFT (GGA-PBE/ultrafine) shielding calculations resulted in an rms chemical-shift distance of 2.8 ppm after lattice including geometry optimization of the diffraction structures by the GIPAW method at GGA-PBE/ultrafine level. Attention is given to the substituted aromatic carbon in the phenyl groups (here forth referred to as the α-carbon) with respect to CSA modeling with electronic methods. The (13)C CSA of this position is accurately determined due to its spectral isolation of the isotropic shift that limits overlap in the FIREMAT spectrum. In cases where the bridging ring is sp(3) carbon, the current density is reduced from extending beyond the peripheral phenyl groups; this plays a significant role in the magnetic shielding of the α-position. Nuclear independent chemical-shift calculations based on GIAO DFT (B3LYP/6-31G(d)) shielding calculations were used to model the intramolecular π-interactions in dianthracene and triptycene. These NICS results estimate the isotropic shift of the α-position in dianthracene to be insignificantly affected by the presence of the neighboring aromatic rings. However, a notable change in isotropic shielding, Δσ(iso)=-2.1 ppm, is predicted for the α- position of triptycene. Experimentally, the δ22 principal component at the �

Application of spin-exchange relaxation-free magnetometry to the Cosmic Axion Spin Precession Experiment

NASA Astrophysics Data System (ADS)

Wang, Tao; Kimball, Derek F. Jackson; Sushkov, Alexander O.; Aybas, Deniz; Blanchard, John W.; Centers, Gary; Kelley, Sean R. O.'; Wickenbrock, Arne; Fang, Jiancheng; Budker, Dmitry

2018-03-01

The Cosmic Axion Spin Precession Experiment (CASPEr) seeks to measure oscillating torques on nuclear spins caused by axion or axion-like-particle (ALP) dark matter via nuclear magnetic resonance (NMR) techniques. A sample spin-polarized along a leading magnetic field experiences a resonance when the Larmor frequency matches the axion/ALP Compton frequency, generating precessing transverse nuclear magnetization. Here we demonstrate a Spin-Exchange Relaxation-Free (SERF) magnetometer with sensitivity ≈ 1 fT /√{ Hz } and an effective sensing volume of 0.1 cm3 that may be useful for NMR detection in CASPEr. A potential drawback of SERF-magnetometer-based NMR detection is the SERF's limited dynamic range. Use of a magnetic flux transformer to suppress the leading magnetic field is considered as a potential method to expand the SERF's dynamic range in order to probe higher axion/ALP Compton frequencies.

Recipes for lateral spin transport between magnetic contacts, advantage of carbon-based materials.

NASA Astrophysics Data System (ADS)

Fert, Albert

2010-03-01

After the presentation of magneto-transport results [1] on metallic carbon nanotubes (CNT) between LSMO electrodes (MR 60-70%, [VAP -- VP] 60mV), I will discuss the general problem of spin transport in a nonmagnetic lateral channel between spin-polarized contacts in both the diffusive and ballistic regimes. In the diffusive regime, a treatment by the classical drift-diffusion equations applied to a multi-terminal structure is used to calculate what can be expected for the output signal with local or non-local voltage probes. A general result is that the output signal (δR = δV/I where δV is the local or non-local output voltage), directly related to the spin accumulation splitting in the channel, scales with the smallest of the relevant spin and interfaces resistances. In the best situation, that is with only tunnel contacts having the same (large) resistance RT and separated by less than the spin diffusion length (λ) in a lateral channel limited to the zone of the contacts, the signal δR increases in proportion of RT as long as the dwell time is smaller than the spin lifetime. δR can be thus much larger than the spin resistance of the channel (product of its resistivity by the ratio λ/section ). This explain why, in the experiments of Ref.[1] on CNT, δR can be as large as 90 Mφ, that is of the order of the tunnel contact resistances and much larger than the spin resistance of the CNT (smaller signals in experiments with CNT or graphene are often due the leak of spin accumulation in lateral channels extending too far outside the contacts). The relative disadvantage for semiconductors comes from the too long dwell time due to much smaller electron velocities than in metallic CNTs (and graphene). We will conclude by a similar analysis of the ballistic regime and a discussion of experiments with graphene. [4pt] [1] Hueso et al, Nature 445, 410 (2007).

Infrared laser spectroscopy of the linear C13 carbon cluster

NASA Technical Reports Server (NTRS)

Giesen, T. F.; Van Orden, A.; Hwang, H. J.; Fellers, R. S.; Provencal, R. A.; Saykally, R. J.

1994-01-01

The infrared absorption spectrum of a linear, 13-atom carbon cluster (C13) has been observed by using a supersonic cluster beam-diode laser spectrometer. Seventy-six rovibrational transitions were measured near 1809 wave numbers and assigned to an antisymmetric stretching fundamental in the 1 sigma g+ ground state of C13. This definitive structural characterization of a carbon cluster in the intermediate size range between C10 and C20 is in apparent conflict with theoretical calculations, which predict that clusters of this size should exist as planar monocyclic rings.

Calibration of the carbon isotope composition (δ13C) of benthic foraminifera

NASA Astrophysics Data System (ADS)

Schmittner, Andreas; Bostock, Helen C.; Cartapanis, Olivier; Curry, William B.; Filipsson, Helena L.; Galbraith, Eric D.; Gottschalk, Julia; Herguera, Juan Carlos; Hoogakker, Babette; Jaccard, Samuel L.; Lisiecki, Lorraine E.; Lund, David C.; Martínez-Méndez, Gema; Lynch-Stieglitz, Jean; Mackensen, Andreas; Michel, Elisabeth; Mix, Alan C.; Oppo, Delia W.; Peterson, Carlye D.; Repschläger, Janne; Sikes, Elisabeth L.; Spero, Howard J.; Waelbroeck, Claire

2017-06-01

The carbon isotope composition (δ13C) of seawater provides valuable insight on ocean circulation, air-sea exchange, the biological pump, and the global carbon cycle and is reflected by the δ13C of foraminifera tests. Here more than 1700 δ13C observations of the benthic foraminifera genus Cibicides from late Holocene sediments (δ13CCibnat) are compiled and compared with newly updated estimates of the natural (preindustrial) water column δ13C of dissolved inorganic carbon (δ13CDICnat) as part of the international Ocean Circulation and Carbon Cycling (OC3) project. Using selection criteria based on the spatial distance between samples, we find high correlation between δ13CCibnat and δ13CDICnat, confirming earlier work. Regression analyses indicate significant carbonate ion (-2.6 ± 0.4) × 10-3‰/(μmol kg-1) [CO32-] and pressure (-4.9 ± 1.7) × 10-5‰ m-1 (depth) effects, which we use to propose a new global calibration for predicting δ13CDICnat from δ13CCibnat. This calibration is shown to remove some systematic regional biases and decrease errors compared with the one-to-one relationship (δ13CDICnat = δ13CCibnat). However, these effects and the error reductions are relatively small, which suggests that most conclusions from previous studies using a one-to-one relationship remain robust. The remaining standard error of the regression is generally σ ≅ 0.25‰, with larger values found in the southeast Atlantic and Antarctic (σ ≅ 0.4‰) and for species other than Cibicides wuellerstorfi. Discussion of species effects and possible sources of the remaining errors may aid future attempts to improve the use of the benthic δ13C record.

δ 13C variation in scallop shells: Increasing metabolic carbon contribution with body size?

NASA Astrophysics Data System (ADS)

Lorrain, Anne; Paulet, Yves-Marie; Chauvaud, Laurent; Dunbar, Robert; Mucciarone, David; Fontugne, Michel

2004-09-01

We examined δ 13C values of shallow and deep-water scallop shells as well as δ 13C of dissolved inorganic carbon (DIC) from the Bay of Brest in western Brittany. Time series of shell calcite δ 13C do not reflect seasonal variation in seawater δ 13C, but rather show a consistent pattern of decreasing δ 13C with age, suggesting a metabolic effect rather than direct environmental control. This δ 13C trend reflects an increasing contribution of metabolic CO 2 to skeletal carbonate throughout ontogeny, although this respired CO 2 does not seem to be the major source of skeletal carbon (contribution of only 10% over the first year of life). We propose a model of this effect that depends on the availability of metabolic carbon relative to the carbon requirements for calcification. A ratio of "respired to precipitated carbon" is calculated, and represents the amount of metabolic carbon available for calcification. Interestingly, this ratio increases throughout ontogeny suggesting a real increase of metabolic carbon utilization into the skeleton relative to carbon from seawater DIC. This ratio allows us to separate two different populations of Pecten maximus of different water depth. It is therefore suggested that shell δ 13C might be used to track differences in the metabolic activity of scallops from different populations.

Preparation and Rate Capability of Carbon Coated LiNi1/3Co1/3Mn1/3O2 as Cathode Material in Lithium Ion Batteries.

PubMed

Yang, Chaofan; Zhang, Xiaosong; Huang, Mengyi; Huang, Junjie; Fang, Zebo

2017-04-12

LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM) is regarded as a promising material for next-generation lithium ion batteries due to the high capacity, but its practical applications are limited by the poor electronic conductivity. Here, a one-step method is used to prepare carbon coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM/C) by applying active carbon as reaction matrix. TEM shows LiNi 1/3 Co 1/3 Mn 1/3 O 2 particles are homogeneously coated by carbon with a thickness about 10 nm. NCM/C delivers the discharge capacity of 191.2 mAh g -1 at 0.5 C (85 mA g -1 ) with a columbic efficiency of 91.1%. At 40 C (6800 mA g -1 ), the discharge capacity of NCM/C is 54.6 mAh g -1 , whereas NCM prepared through sol-gel route only delivers 13.2 mAh g -1 . After 100 charge and discharge cycles at 1 C (170 mA g -1 ) the capacity retention is 90.3% for NCM/C, whereas it is only 72.4% for NCM. The superior charge/discharge performance of NCM/C owes much to the carbon coating layer, which is not only helpful to increase the electronic conductivity but also contributive to inhibit the side reactions between LiNi 1/3 Co 1/3 Mn 1/3 O 2 and the liquid electrolyte.

Effect of hyperfine-induced spin mixing on the defect-enabled spin blockade and spin filtering in GaNAs

NASA Astrophysics Data System (ADS)

Puttisong, Y.; Wang, X. J.; Buyanova, I. A.; Chen, W. M.

2013-03-01

The effect of hyperfine interaction (HFI) on the recently discovered room-temperature defect-enabled spin-filtering effect in GaNAs alloys is investigated both experimentally and theoretically based on a spin Hamiltonian analysis. We provide direct experimental evidence that the HFI between the electron and nuclear spin of the central Ga atom of the spin-filtering defect, namely, the Gai interstitials, causes strong mixing of the electron spin states of the defect, thereby degrading the efficiency of the spin-filtering effect. We also show that the HFI-induced spin mixing can be suppressed by an application of a longitudinal magnetic field such that the electronic Zeeman interaction overcomes the HFI, leading to well-defined electron spin states beneficial to the spin-filtering effect. The results provide a guideline for further optimization of the defect-engineered spin-filtering effect.

Spin disorder in maghemite nanoparticles investigated using polarized neutrons and nuclear resonant scattering

NASA Astrophysics Data System (ADS)

Herlitschke, M.; Disch, S.; Sergueev, I.; Schlage, K.; Wetterskog, E.; Bergström, L.; Hermann, R. P.

2016-04-01

The manuscript reports the investigation of spin disorder in maghemite nanoparticles of different shape by a combination of polarized small-angle neutron scattering (SANSPOL) and nuclear forward scattering (NFS) techniques. Both methods are sensitive to magnetization on the nanoscale. SANSPOL allows for investigation of the particle morphology and spatial magnetization distribution and NFS extends this nanoscale information to the atomic scale, namely the orientation of the hyperfine field experienced by the iron nuclei. The studied nanospheres and nanocubes with diameters of 7.4 nm and 10.6 nm, respectively, exhibit a significant spin disorder. This effect leads to a reduction of the magnetization to 44% and 58% of the theoretical maghemite bulk value, observed consistently by both techniques.

Spinning angle optical calibration apparatus

DOEpatents

Beer, Stephen K.; Pratt, II, Harold R.

1991-01-01

An optical calibration apparatus is provided for calibrating and reproducing spinning angles in cross-polarization, nuclear magnetic resonance spectroscopy. An illuminated magnifying apparatus enables optical setting an accurate reproducing of spinning "magic angles" in cross-polarization, nuclear magnetic resonance spectroscopy experiments. A reference mark scribed on an edge of a spinning angle test sample holder is illuminated by a light source and viewed through a magnifying scope. When the "magic angle" of a sample material used as a standard is attained by varying the angular position of the sample holder, the coordinate position of the reference mark relative to a graduation or graduations on a reticle in the magnifying scope is noted. Thereafter, the spinning "magic angle" of a test material having similar nuclear properties to the standard is attained by returning the sample holder back to the originally noted coordinate position.

Carbon-Carbon Recuperators in Closed-Brayton-Cycle Nuclear Space Power Systems: A Feasibility Assessment

NASA Technical Reports Server (NTRS)

Barrett, Michael J.; Johnson, Paul K.

2004-01-01

The feasibility of using carbon-carbon recuperators in closed-Brayton-cycle (CBC) nuclear space power conversion systems (PCS) was assessed. Recuperator performance expectations were forecast based on projected thermodynamic cycle state values for a planetary mission. Resulting thermal performance, mass and volume for a plate-fin carbon-carbon recuperator were estimated and quantitatively compared with values for a conventional offset-strip-fin metallic design. Material compatibility issues regarding carbon-carbon surfaces exposed to the working fluid in the CBC PCS were also discussed.

13C Nuclear magnetic resonance studies of kerogen from Cretaceous black shales thermally altered by basaltic intrusions and laboratory simulations

USGS Publications Warehouse

Dennis, L.W.; Maciel, G.E.; Hatcher, P.G.; Simoneit, B.R.T.

1982-01-01

Cretaceous black shales from DSDP Leg 41, Site 368 in the Eastern Atlantic Ocean were thermally altered during the Miocene by an intrusive basalt. The sediments overlying and underlying the intrusive body were subjected to high temperatures (up to ~ 500??C) and, as a result, their kerogen was significantly altered. The extent of this alteration has been determined by examination by means of 13C nuclear magnetic resonance, using cross polarization/magic-angle spinning (CP/MAS). Results indicate that the kerogen becomes progressively more aromatic in the vicinity of the intrusive body. Laboratory heating experiments, simulating the thermal effects of the basaltic intrusion, produced similar results on unaltered shale from the drill core. The 13C CP/MAS results appear to provide a good measure of thermal alteration. ?? 1982.

Toward Quantum Non-demolition of nitrogen-vacancy centers in diamond

NASA Astrophysics Data System (ADS)

Hodges, Jonathan; Jiang, Liang; Maze, Jeronimo; Lukin, Mikhail

2009-05-01

The nitrogen-vacancy color center (NVC) in diamond, which possesses a long-lived electronic spin (S=1) ground state with optical addressability, is a promising platform for quantum networks, single-photon sources, and nanoscale magnetometers. Here, we make use of a nuclear spin based quantum memory to demonstrate quantum non-demolition measurement of a solid-state spin qubit. By entangling the electron spin with a polarized carbon-13 spin (I=1/2) in the lattice, we have repeated optical measurement of the electron spin for the polarization lifetime of the nuclear spin. We show relative improvements in signal-to-noise of greater than 300%. These techniques can be used to improve the sensitivity of NVC magnetometers.

Nuclear magnetic relaxation induced by exchange-mediated orientational randomization: longitudinal relaxation dispersion for a dipole-coupled spin-1/2 pair.

PubMed

Chang, Zhiwei; Halle, Bertil

2013-10-14

In complex biological or colloidal samples, magnetic relaxation dispersion (MRD) experiments using the field-cycling technique can characterize molecular motions on time scales ranging from nanoseconds to microseconds, provided that a rigorous theory of nuclear spin relaxation is available. In gels, cross-linked proteins, and biological tissues, where an immobilized macromolecular component coexists with a mobile solvent phase, nuclear spins residing in solvent (or cosolvent) species relax predominantly via exchange-mediated orientational randomization (EMOR) of anisotropic nuclear (electric quadrupole or magnetic dipole) couplings. The physical or chemical exchange processes that dominate the MRD typically occur on a time scale of microseconds or longer, where the conventional perturbation theory of spin relaxation breaks down. There is thus a need for a more general relaxation theory. Such a theory, based on the stochastic Liouville equation (SLE) for the EMOR mechanism, is available for a single quadrupolar spin I = 1. Here, we present the corresponding theory for a dipole-coupled spin-1/2 pair. To our knowledge, this is the first treatment of dipolar MRD outside the motional-narrowing regime. Based on an analytical solution of the spatial part of the SLE, we show how the integral longitudinal relaxation rate can be computed efficiently. Both like and unlike spins, with selective or non-selective excitation, are treated. For the experimentally important dilute regime, where only a small fraction of the spin pairs are immobilized, we obtain simple analytical expressions for the auto-relaxation and cross-relaxation rates which generalize the well-known Solomon equations. These generalized results will be useful in biophysical studies, e.g., of intermittent protein dynamics. In addition, they represent a first step towards a rigorous theory of water (1)H relaxation in biological tissues, which is a prerequisite for unravelling the molecular basis of soft

A new high pressure sapphire nuclear magnetic resonance cell

NASA Astrophysics Data System (ADS)

Bai, Shi; Taylor, Craig M.; Mayne, Charles L.; Pugmire, Ronald J.; Grant, David M.

1996-01-01

A new version of a single-crystal sapphire high pressure nuclear magnetic resonance (NMR) cell is described that is capable of controlling the sample pressure independent of the temperature. A movable piston inside the cell adjusts and controls the sample pressure from ambient conditions to 200 atm within ±0.3 atm. The linewidth at half-height for a 13C spectrum of carbon dioxide at 15 °C and 57.8 atm is found to be 0.5 Hz. The carbon dioxide gas/liquid phase transition is clearly observed by measuring 13C chemical shifts as the sample pressure approaches equilibrium. The time required for this NMR cell to reach equilibrium with its surroundings is relatively short, usually 15-30 min. The cell body has the same outer dimensions of a standard spinning turbine and fits into a standard 10 mm commercial probehead capable of controlling the sample temperature using the spectrometer's variable temperature unit. The flexibility of the device and the increased speed in making the measurement is demonstrated. Such control of important thermodynamic variables facilitates the NMR study of important biochemical and chemical reactions in gas, liquid, and supercritical fluid environments.

Proceedings of the 13th biennial conference on carbon. Extended abstracts and program

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1977-01-01

Properties of carbon are covered including: mechanical and frictional properties; chemical reactivity and surfaces; aerospace applications; carbonization and graphitization; industrial applications; electrical and thermal properties; biomaterials applications; fibers and composites; nuclear applications; activated carbon and adsorption; advances in carbon characterization; and micromechanics and modeling. (GHT)

Potent and selective inhibitors of 11β-hydroxysteroid dehydrogenase type 1 labeled with carbon-13 and carbon-14.

PubMed

Latli, Bachir; Hrapchak, Matt; Savoie, Jolaine; Zhan, Yongda; Busacca, Carl A; Senanayake, Chris H

2017-07-01

(S)-6-(2-Hydroxy-2-methylpropyl)-3-((S)-1-(4-(1-methyl-2-oxo-1,2-dihydropyridin-4-yl)phenyl)ethyl)-6-phenyl-1,3-oxazinan-2-one (1) and (4aR,9aS)-1-(1H-benzo[d]midazole-5-carbonyl)-2,3,4,4a,9,9a-hexahydro-1-H-indeno[2,1-b]pyridine-6-carbonitrile hydrochloride (2) are potent and selective inhibitor of 11β-hydroxysteroid dehydrogenase type 1 enzyme. These 2 drug candidates developed for the treatment of type-2 diabetes were prepared labeled with carbon-13 and carbon-14 to enable drug metabolism, pharmacokinetics, bioanalytical, and other studies. In the carbon-13 synthesis, benzoic- 13 C 6 acid was converted in 7 steps and in 16% overall yield to [ 13 C 6 ]-(1). Aniline- 13 C 6 was converted in 7 steps to 1H-benzimidazole-1-2,3,4,5,6- 13 C 6 -5-carboxylic acid and then coupled to a tricyclic chiral indenopiperidine to afford [ 13 C 6 ]-(2) in 19% overall yield. The carbon-14 labeled (1) was prepared efficiently in 2 radioactive steps in 41% overall yield from an advanced intermediate using carbon-14 labeled methyl magnesium iodide and Suzuki-Miyaura cross coupling via in situ boronate formation. As for the synthesis of [ 14 C]-(2), 1H-benzimidazole-5-carboxylic- 14 C acid was first prepared in 4 steps using potassium cyanide- 14 C, then coupled to the chiral indenopiperidine using amide bond formation conditions in 26% overall yield. Copyright © 2017 John Wiley & Sons, Ltd.

Proton-decoupled, Overhauser-enhanced, spatially localized carbon-13 spectroscopy in humans.

PubMed

Bottomley, P A; Hardy, C J; Roemer, P B; Mueller, O M

1989-12-01

Spatially localized, natural abundance, carbon (13C) NMR spectroscopy has been combined with proton (1H) decoupling and nuclear Overhauser enhancement to improve 13C sensitivity up to five-fold in the human leg, liver, and heart. Broadhand-decoupled 13C spectra were acquired in 1 s to 17 min with a conventional 1.5-T imaging/spectroscopy system, an auxiliary 1H decoupler, an air-cooled dual-coil coplanar surface probe, and both depth-resolved surface coil spectroscopy (DRESS) and one-dimensional phase-encoding gradient NMR pulse sequences. The surface coil probe comprised circular and figure-eight-shaped coils to eliminate problems with mutual coupling of coils at high decoupling power levels applied during 13C reception. Peak decoupler RF power deposition in tissue was computed numerically from electromagnetic theory assuming a semi-infinite plane of uniform biological conductor. Peak values at the surface were calculated at 4 to 6 W/kg in any gram of tissue for each watt of decoupler power input excluding all coil and cable losses, warning of potential local RF heating problems in these and related experiments. The average power deposition was about 9 mW/kg per watt input, which should present no systemic hazard. At 3 W input, human 13C spectra were decoupled to a depth of about 5 cm while some Overhauser enhancement was sustained up to about 3 cm depth, without ill effect. The observation of glycogen in localized natural abundance 13C spectra of heart and muscle suggests that metabolites in the citric acid cycle should be observable noninvasively using 13C-labeled substrates.

Double line groups: structure, irreducible representations and spin splitting of the bands

NASA Astrophysics Data System (ADS)

Lazić, N.; Milivojević, M.; Vuković, T.; Damnjanović, M.

2018-06-01

Double line groups are derived, structurally examined and classified within 13 infinite families. Their irreducible representations, found and tabulated, single out the complete set of conserved quantum numbers in fermionic quasi-one-dimensional systems possessing either translational periodicity or incommensurate helical symmetry. Spin–orbit interaction is analyzed: the induced orbital band splitting and the consequent removal of the spin degeneracy are completely explained. Being incompatible with vertical mirror symmetry, as well as with simultaneous invariance under time-reversal and horizontal (roto)reflections, spin splitting and spin polarized currents may occur only in the systems with the first and the fifth family double line group symmetry. The effects are illustrated on carbon nanotubes.

Spin coherence and 14N ESEEM effects of nitrogen-vacancy centers in diamond with X-band pulsed ESR

NASA Astrophysics Data System (ADS)

Rose, B. C.; Weis, C. D.; Tyryshkin, A. M.; Schenkel, T.; Lyon, S. A.

2017-02-01

Pulsed ESR experiments are reported for ensembles of negatively-charged nitrogen-vacancy centers (NV$^-$) in diamonds at X-band magnetic fields (280-400 mT) and low temperatures (2-70 K). The NV$^-$ centers in synthetic type IIb diamonds (nitrogen impurity concentration $<1$~ppm) are prepared with bulk concentrations of $2\\cdot 10^{13}$ cm$^{-3}$ to $4\\cdot 10^{14}$ cm$^{-3}$ by high-energy electron irradiation and subsequent annealing. We find that a proper post-radiation anneal (1000$^\\circ$C for 60 mins) is critically important to repair the radiation damage and to recover long electron spin coherence times for NV$^-$s. After the annealing, spin coherence times of T$_2 = 0.74$~ms at 5~K are achieved, being only limited by $^{13}$C nuclear spectral diffusion in natural abundance diamonds. At X-band magnetic fields, strong electron spin echo envelope modulation (ESEEM) is observed originating from the central $^{14}$N nucleus. The ESEEM spectral analysis allows for accurate determination of the $^{14}$N nuclear hypefine and quadrupole tensors. In addition, the ESEEM effects from two proximal $^{13}$C sites (second-nearest neighbor and fourth-nearest neighbor) are resolved and the respective $^{13}$C hyperfine coupling constants are extracted.

Apportioning carbon sources of authigenic carbonate of extremely 13C-depleted foraminifera from the western North Pacific sediments: Implication from the coupled 13C and 14C isotopic mass balance approach

NASA Astrophysics Data System (ADS)

Uchida, M.; Ohkushi, K.; Ahagon, N.; Kimoto, K.; Inagaki, F.; Shibata, Y.

2005-12-01

Recently, Uchida et al. (G-cubed, 2004) and Ohkushi et al. (G-cubed, 2005) interprete /delta 13C variations of planktonic and benthic foraminifera found in Last Glacial sediments in off Shimokita Peninsula and Tokachi as evidence for periodic releases of methane, arising from the dissociation of methane hydrate, and its subsequent oxidation in bottom- and/or surface-water environments. According to recent observations of anomalous bottom-simulating reflections, northwest Pacific marginal sediments around Japan main islands bear large abundances of methane hydrate. In this study, analyzed piston cores (42° 21.42' N, 144° 13.36' E) at a water depth 1066-m was retrieved from the off Tokachi continental slope in the Oyashio current region, where recently is found to bear immense amounts of methane hydrate. The piston core covered past 22 ka with high-resolution. Here we showed that carbon isotope signals indicated that planktonic and benthic foraminifera in several glacial sediment layers in the core were highly depleted in13 C; both the planktonic and benthic foraminiferal /delta 13C values ranged from about -10/permil to -2/permil. Most foraminiferal tests in these horizons were brown as a result of postdepositional alteration. Foraminiferal oxygen isotopes fluctuated abnormally in the glacial sediment layers, showing small (about 0.5/permil) positive shifts relative to normal glacial values. We attributed the positive shifts to authigenic carbonate formation in the foraminiferal tests. In order to decipher the relation between foraminifera carbon isotopic signal and methane release from the seafloor, we have apportioned carbon sources (methane from methane hydrate or not) of foraminiferal carbon isotopic anomalies using dual mass balance isotopic model (14C/ 12C and 13C/ 12C). It has been suggested that sulfate-dependent anaerobic methane oxidation (AOM) dominates carbon oxidation and attendant authigenic carbonate precipitation to foraminifera. To this assumption

The oceanic carbon cycle implicated in the d13Ccarb and the d13Corg variations from the terminal Ediacaran to the Early Cambrian

NASA Astrophysics Data System (ADS)

Ishikawa, T.; Ueno, Y.; Komiya, T.; Shu, D.; Li, Y.; Yoshida, N.; Maruyama, S.

2009-04-01

The terminal Neoproterozoic and its transition into the Cambrian witnessed major evolutionary and geochemical changes (e.g. Knoll, 1994). Evolutionary features include extinction and subsequent radiation events (e.g. Brasier, 1994; Knoll, 1994; Knoll and Carroll, 1999; Shu 2008). Geochemical changes comprise secular variations of the global carbon cycle expressed as variations of the d13C isotope records. A representative d13C curve for inorganic carbon (d13Ccarb) across the Precambrian/Cambrian boundary (Pc/C boundary) shows the existence of large fluctuations (e.g. Kirschvink et al., 1991; Narbonne et al., 1994; Kaufman et al., 1995; Amthor et al., 2003; Maloof et al., 2005, Ishikawa et al., 2008). This indicates a significant change of the oceanic carbon cycle at that time. On the other hand, the d13C values for total organic carbon (d13Corg) have rarely been reported together with the d13Ccarb across the boundary. Therefore, the precise relation between the d13Ccarb and the d13Corg and the global carbon cycle at the Pc/C boundary are still ambiguous. This work presents a first high-resolution d13Corg chemostratigraphy of drill core samples across the Pc/C boundary in the Three Gorges area, South China. Based on the results, this work additionally proposes variations of the sizes of the oceanic carbon reservoirs by a calculation of the carbon cycle model at the Pc/C boundary. The Three Gorges section extends from the uppermost Ediacaran dolostone (Dengying Formation), through the lowermost Early Cambrian muddy limestone (Yanjiahe Formation) to the middle Early Cambrian calcareous black shale (Shuijingtuo Formation). The ^13Corg values exhibit relatively invariant values averaging at -31 permil. By comparison between the d13Ccarb and d13Corg, we recognize two different terms in this period. The first term from the Pc/C boundary to the early Nemakit-Daldynian (ND) is characterized by the decoupling of d13Corg and d13Ccarb, stable d13Corg and the significant

The complete set of spin observables for the (13)C(polarized proton, polarized neutron)(13)N and (15)N(polarized proton, polarized neutron)(15)O reactions

NASA Astrophysics Data System (ADS)

Du, Qun Qun

1998-12-01

The 13C(p,n)13N and 15N(p,n)15O reactions have been a puzzle for more than ten years. The ground state transitions are Jπ=1/2- to Jπ=1/2-. These are 'mixed' transitions because they can involve quantum number changes either (/Delta T=1,/ /Delta J=0,/ /Delta/pi=0,/ /Delta S=0), or (/Delta T=1,/ /Delta J=1,/ /Delta/pi=0,/ /Delta S=1); these quantum number changes are refered to as 'Fermi' and 'Gamow-Teller' respectively. Because the quantum number changes are the same as for Fermi and Gamow-Teller beta decay. From the systematics of (p,n) and (n,p) reactions on pure Fermi transitions (e.g. 0 + to 0+) and pure Gamow-Teller transitions (e.g. 0+ to 1+), calibrations have been established of cross section per unit B(F) or unit B(GT), where 'B' refers to doubly reduced matrix elements extracted from beta decay. However, cross sections for the 13C(p,n)13N(g.s.) and 15N(p,n)15O(g.s.) reactions are substantially larger than one would then predict from the known B(F)s and B(GT)s for these transitions. To explore this anomaly, spin observables were used to extract separately the Fermi and Gamow-Teller cross sections for these reactions. To acquire the complete sets of polarization- transfer observables, a new neutron polarimeter was designed, built, commissioned and calibrated. This polarimeter, call the '2π polarimeter' because of its complete azimuthal coverage for scattered neutrons, has very good position and timing resolution (354 ps). The complete sets of spin-transfer coefficients Dij for 13C(p,n)13N (at 0o , 5.5o , and 11o ) and 15N(p,n)15O (at 0o ) at 135 MeV were measured. Following the formalism of Ichimura and Kawahigashi, we extracted the spin-longitudinal, and spin-transverse and spin-independent responses D0,/ Dq,/ Dn and Dp from the measured Dijs. The F and GT fractions of the (p,n) cross sections are then extracted as f F=D0 and fGT=Dn+Dp+Dq=1- d0. Values of Dk for both the 13C(p,n)13N(g.s) and 15N(p,n)15O(g.s.) were extracted. From these responses, we

Irrigation, fertilization and initial substrate quality effects on decomposing Loblolly pine litter chemistry

Treesearch

Felipe G. Sanchez

2004-01-01

Changes in carbon chemistry (i.e., carbon compound classes such as aromatics, phenolics, etc.) of loblolly pine (Pinus taeda L.) litter were examined during three years of decomposition under factorial combinations of irrigation and fertilization treatments. Cross polarization magic angle spinning 13C nuclear magnetic resonance...

Spinning angle optical calibration apparatus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beer, S.K.; Pratt, H.R. II.

1989-09-12

An optical calibration apparatus is provided for calibrating and reproducing spinning angles in cross-polarization, nuclear magnetic resonance spectroscopy. An illuminated magnifying apparatus enables optical setting and accurate reproducing of spinning magic angles in cross-polarization, nuclear magnetic resonance spectroscopy experiments. A reference mark scribed on an edge of a spinning angle test sample holder is illuminated by a light source and viewed through a magnifying scope. When the magic angle of a sample material used as a standard is attained by varying the angular position of the sample holder, the coordinate position of the reference mark relative to a graduation ormore » graduations on a reticle in the magnifying scope is noted. Thereafter, the spinning magic angle of a test material having similar nuclear properties to the standard is attained by returning the sample holder back to the originally noted coordinate position. 2 figs.« less

Relaxation-optimized transfer of spin order in Ising spin chains

NASA Astrophysics Data System (ADS)

Stefanatos, Dionisis; Glaser, Steffen J.; Khaneja, Navin

2005-12-01

In this paper, we present relaxation optimized methods for the transfer of bilinear spin correlations along Ising spin chains. These relaxation optimized methods can be used as a building block for the transfer of polarization between distant spins on a spin chain, a problem that is ubiquitous in multidimensional nuclear magnetic resonance spectroscopy of proteins. Compared to standard techniques, significant reduction in relaxation losses is achieved by these optimized methods when transverse relaxation rates are much larger than the longitudinal relaxation rates and comparable to couplings between spins. We derive an upper bound on the efficiency of the transfer of the spin order along a chain of spins in the presence of relaxation and show that this bound can be approached by the relaxation optimized pulse sequences presented in the paper.

Electron-nuclear spin dynamics of Ga centers in GaAsN dilute nitride semiconductors probed by pump-probe spectroscopy

NASA Astrophysics Data System (ADS)

Sandoval-Santana, J. C.; Ibarra-Sierra, V. G.; Azaizia, S.; Carrère, H.; Bakaleinikov, L. A.; Kalevich, V. K.; Ivchenko, E. L.; Marie, X.; Amand, T.; Balocchi, A.; Kunold, A.

2018-03-01

We propose an experimental procedure to track the evolution of electronic and nuclear spins in Ga2+ centers in GaAsN dilute semiconductors. The method is based on a pump-probe scheme that enables to monitor the time evolution of the three components of the electronic and nuclear spin variables. In contrast to other characterization methods, as nuclear magnetic resonance, this one only needs moderate magnetic fields (B≈ 10 mT), and does not require microwave irradiation. Specifically, we carry out a series of tests for different experimental conditions in order to optimize the procedure for maximum sensitivity in the measurement of the circular degree of polarization. Based on previous experimental results and the theoretical calculations presented here, we estimate that the method could yield a time resolution of about 10ps.

Spin disorder in maghemite nanoparticles investigated using polarized neutrons and nuclear resonant scattering

DOE PAGES

Herlitschke, Marcus; Disch, Sabrina; Sergueev, I.; ...

2016-05-11

The manuscript reports the investigation of spin disorder in maghemite nanoparticles of different shape by a combination of polarized small-angle neutron scattering (SANSPOL) and nuclear forward scattering (NFS) techniques. Both methods are sensitive to magnetization on the nanoscale. SANSPOL allows for investigation of the particle morphology and spatial magnetization distribution and NFS extends this nanoscale information to the atomic scale, namely the orientation of the hyperfine field experienced by the iron nuclei. The studied nanospheres and nanocubes with diameters of 7.4nm and 10.6 nm, respectively, exhibit a significant spin disorder. This effect leads to a reduction of the magnetization tomore » 44% and 58% of the theoretical maghemite bulk value, observed consistently by both techniques.« less

Spin disorder in maghemite nanoparticles investigated using polarized neutrons and nuclear resonant scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herlitschke, Marcus; Disch, Sabrina; Sergueev, I.

The manuscript reports the investigation of spin disorder in maghemite nanoparticles of different shape by a combination of polarized small-angle neutron scattering (SANSPOL) and nuclear forward scattering (NFS) techniques. Both methods are sensitive to magnetization on the nanoscale. SANSPOL allows for investigation of the particle morphology and spatial magnetization distribution and NFS extends this nanoscale information to the atomic scale, namely the orientation of the hyperfine field experienced by the iron nuclei. The studied nanospheres and nanocubes with diameters of 7.4nm and 10.6 nm, respectively, exhibit a significant spin disorder. This effect leads to a reduction of the magnetization tomore » 44% and 58% of the theoretical maghemite bulk value, observed consistently by both techniques.« less

NMR studies of spin dynamics in cuprates

NASA Astrophysics Data System (ADS)

Takigawa, M.; Mitzi, D. B.

1994-04-01

We report recent NMR results in cuprates. The oxygen Knight shift and the Cu nuclear spin-lattice relaxation rate in Bi2.1Sr1.94Ca0.88Cu2.07O8+δ single crystals revealed a gapless superconducting state, which can be most naturally explained by a d-wave pairing state and the intrinsic disorder in this material. The Cu nuclear spin-spin relaxation rate in underdoped YBa2Cu3O6.63 shows distinct temperature dependence from the spin-lattice relaxation rate, providing direct evidence for a pseudo spin-gap near the antiferromagnetic wave vector.

Electron-spin-resonance studies of vapor-grown carbon fibers

NASA Technical Reports Server (NTRS)

Marshik, B.; Meyer, D.; Apple, T.

1987-01-01

The effects of annealing temperature and fiber diameter on the degree of disorder of vapor-grown carbon fibers were investigated by analyzing the electron-spin-resonance (ESR) line shapes of fibers annealed at six various temperatures up to 3375 K. The diameter of fibers, grown from methane gas, ranged from 10 to 140 microns with most fibers between 20 and 50 microns. It was found that the degree of disorder of vapor-grown fibers decreases upon annealing to higher temperature; standard angular deviation between the fiber axis and the crystallite basal planes could vary from 35 deg (for annealing temperature of 2275 K) to 12 deg (for 3375 K). With respect to fiber diameter, order parameters were found to be higher for fibers of smaller diameters.

Towards quantum networks of single spins: analysis of a quantum memory with an optical interface in diamond.

PubMed

Blok, M S; Kalb, N; Reiserer, A; Taminiau, T H; Hanson, R

2015-01-01

Single defect centers in diamond have emerged as a powerful platform for quantum optics experiments and quantum information processing tasks. Connecting spatially separated nodes via optical photons into a quantum network will enable distributed quantum computing and long-range quantum communication. Initial experiments on trapped atoms and ions as well as defects in diamond have demonstrated entanglement between two nodes over several meters. To realize multi-node networks, additional quantum bit systems that store quantum states while new entanglement links are established are highly desirable. Such memories allow for entanglement distillation, purification and quantum repeater protocols that extend the size, speed and distance of the network. However, to be effective, the memory must be robust against the entanglement generation protocol, which typically must be repeated many times. Here we evaluate the prospects of using carbon nuclear spins in diamond as quantum memories that are compatible with quantum networks based on single nitrogen vacancy (NV) defects in diamond. We present a theoretical framework to describe the dephasing of the nuclear spins under repeated generation of NV spin-photon entanglement and show that quantum states can be stored during hundreds of repetitions using typical experimental coupling parameters. This result demonstrates that nuclear spins with weak hyperfine couplings are promising quantum memories for quantum networks.

Diamond nitrogen vacancy electronic and nuclear spin-state anti-crossings under weak transverse magnetic fields

NASA Astrophysics Data System (ADS)

Clevenson, Hannah; Chen, Edward; Dolde, Florian; Teale, Carson; Englund, Dirk; Braje, Danielle

2016-05-01

We report on detailed studies of electronic and nuclear spin states in the diamond nitrogen vacancy (NV) center under moderate transverse magnetic fields. We numerically predict and experimentally verify a previously unobserved NV ground state hyperfine anti-crossing occurring at magnetic bias fields as low as tens of Gauss - two orders of magnitude lower than previously reported hyperfine anti-crossings at ~ 510 G and ~ 1000 G axial magnetic fields. We then discuss how this regime can be optimized for magnetometry and other sensing applications and propose a method for how the nitrogen-vacancy ground state Hamiltonian can be manipulated by small transverse magnetic fields to polarize the nuclear spin state. Acknowlegement: The Lincoln Laboratory portion of this work is sponsored by the Assistant Secretary of Defense for Research & Engineering under Air Force Contract #FA8721-05-C-0002. Opinions, interpretations, conclusions and recommendations are those of the authors and are not necessarily endorsed by the United States Government.

Contribution of deep sourced carbon from hydrocarbon seeps to sedimentary organic carbon: Evidence from Δ14C and δ13C isotopes

NASA Astrophysics Data System (ADS)

Feng, D.; Peckmann, J.; Peng, Y.; Liang, Q.; Roberts, H. H.; Chen, D.

2017-12-01

Sulfate-driven anaerobic oxidation of methane (AOM) limits the release of methane from marine sediments and promotes the formation of carbonates close to the seafloor along continental margins. It has been established that hydrocarbon seeps are a source of dissolved inorganic and organic carbon to marine environments. However, questions remain about the contribution of deep sourced carbon from hydrocarbon seeps to the sedimentary organic carbon pool. For a number of hydrocarbon seeps from the South China Sea and the Gulf of Mexico, the portion of modern carbon was determined based on natural radiocarbon abundances (Δ14C) and stable carbon isotope (δ13Corganic carbon) compositions of the non-carbonate fractions extracted from authigenic carbonates. Samples from both areas show a mixing trend between ideal planktonic organic carbon (δ13C = -22‰ VPDB and 90% modern carbon) and the ambient methane. The δ13Corganic carbon values of non-carbonate fractions from three ancient seep deposits (northern Italy, Miocene; western Washington State, USA, Eocene to Oligocene) confirm that the proxy can be used to constrain the record of sulfate-driven AOM through most of Earth history by measuring the δ13C values of organic carbon. This study reveals the potential of using δ13C values of organic carbon to discern seep and non-seep environments. This new approach is particularly promising when authigenic carbonate is not present in ancient sedimentary environments. Acknowledgments: The authors thank BOEM and NOAA for their years' support of the deep-sea dives. Funding was provided by the NSF of China (Grants: 41422602 and 41373085).

Hyperpolarization of Frozen Hydrocarbon Gases by Dynamic Nuclear Polarization at 1.2 K.

PubMed

Vuichoud, Basile; Canet, Estel; Milani, Jonas; Bornet, Aurélien; Baudouin, David; Veyre, Laurent; Gajan, David; Emsley, Lyndon; Lesage, Anne; Copéret, Christophe; Thieuleux, Chloé; Bodenhausen, Geoffrey; Koptyug, Igor; Jannin, Sami

2016-08-18

We report a simple and general method for the hyperpolarization of condensed gases by dynamic nuclear polarization (DNP). The gases are adsorbed in the pores of structured mesoporous silica matrices known as HYPSOs (HYper Polarizing SOlids) that have paramagnetic polarizing agents covalently bound to the surface of the mesopores. DNP is performed at low temperatures and moderate magnetic fields (T = 1.2 K and B0 = 6.7 T). Frequency-modulated microwave irradiation is applied close to the electron spin resonance frequency (f = 188.3 GHz), and the electron spin polarization of the polarizing agents of HYPSO is transferred to the nuclear spins of the frozen gas. A proton polarization as high as P((1)H) = 70% can be obtained, which can be subsequently transferred to (13)C in natural abundance by cross-polarization, yielding up to P((13)C) = 27% for ethylene.

Thermal diffusivity and nuclear spin relaxation: a continuous wave free precession NMR study.

PubMed

Venâncio, Tiago; Engelsberg, Mario; Azeredo, Rodrigo B V; Colnago, Luiz A

2006-07-01

Continuous wave free precession (CWFP) nuclear magnetic resonance is capable of yielding quantitative and easily obtainable information concerning the kinetics of processes that change the relaxation rates of the nuclear spins through the action of some external agent. In the present application, heat flow from a natural rubber sample to a liquid nitrogen thermal bath caused a large temperature gradient leading to a non-equilibrium temperature distribution. The ensuing local changes in the relaxation rates could be monitored by the decay of the CWFP signals and, from the decays, it was possible to ascertain the prevalence of a diffusive process and to obtain an average value for the thermal diffusivity.

In situ measurement of magnesium carbonate formation from CO2 using static high-pressure and -temperature 13C NMR.

PubMed

Surface, J Andrew; Skemer, Philip; Hayes, Sophia E; Conradi, Mark S

2013-01-02

We explore a new in situ NMR spectroscopy method that possesses the ability to monitor the chemical evolution of supercritical CO(2) in relevant conditions for geological CO(2) sequestration. As a model, we use the fast reaction of the mineral brucite, Mg(OH)(2), with supercritical CO(2) (88 bar) in aqueous conditions at 80 °C. The in situ conversion of CO(2) into metastable and stable carbonates is observed throughout the reaction. After more than 58 h of reaction, the sample was depressurized and analyzed using in situ Raman spectroscopy, where the laser was focused on the undisturbed products through the glass reaction tube. Postreaction, ex situ analysis was performed on the extracted and dried products using Raman spectroscopy, powder X-ray diffraction, and magic-angle spinning (1)H-decoupled (13)C NMR. These separate methods of analysis confirmed a spatial dependence of products, possibly caused by a gradient of reactant availability, pH, and/or a reaction mechanism that involves first forming hydroxy-hydrated (basic, hydrated) carbonates that convert to the end-product, anhydrous magnesite. This carbonation reaction illustrates the importance of static (unmixed) reaction systems at sequestration-like conditions.

Abnormal Elasticity of Single-Crystal Magnesiosiderite across the Spin Transition in Earth's Lower Mantle

NASA Astrophysics Data System (ADS)

Fu, Suyu; Yang, Jing; Lin, Jung-Fu

2017-01-01

Brillouin light scattering and impulsive stimulated light scattering have been used to determine the full elastic constants of magnesiosiderite [(Mg0.35Fe0.65)CO3 ] up to 70 GPa at room temperature in a diamond-anvil cell. Drastic softening in C11 , C33 , C12 , and C13 elastic moduli associated with the compressive stress component and stiffening in C44 and C14 moduli associated with the shear stress component are observed to occur within the spin transition between ˜42.4 and ˜46.5 GPa . Negative values of C12 and C13 are also observed within the spin transition region. The Born criteria constants for the crystal remain positive within the spin transition, indicating that the mixed-spin state remains mechanically stable. Significant auxeticity can be related to the electronic spin transition-induced elastic anomalies based on the analysis of Poisson's ratio. These elastic anomalies are explained using a thermoelastic model for the rhombohedral system. Finally, we conclude that mixed-spin state ferromagnesite, which is potentially a major deep-carbon carrier, is expected to exhibit abnormal elasticity, including a negative Poisson's ratio of -0.6 and drastically reduced VP by 10%, in Earth's midlower mantle.

Determination of alkylbenzenesulfonate surfactants in groundwater using macroreticular resins and carbon-13 nuclear magnetic resonance spectrometry

USGS Publications Warehouse

Thurman, E.M.; Willoughby, T.; Barber, L.B.; Thorn, K.A.

1987-01-01

Alkylbenzenesulfonate surfactants were determined in groundwater at concentrations as low as 0.3 mg/L. The method uses XAD-8 resin for concentration, followed by elution with methanol, separation of anionic and nonionic surfactants by anion exchange, quantitation by titration, and identification by 13C nuclear magnetic resonance spectrometry. Laboratory standards and field samples containing straight-chain and branched-chain alkylbenzenesulfonates, sodium dodecyl sulfate, and alkylbenzene ethoxylates were studied. The XAD-8 extraction of surfactants from groundwater was completed in the field, which simplified sample preservation and reduced the cost of transporting samples.

Spin noise spectroscopy of donor-bound electrons in ZnO

NASA Astrophysics Data System (ADS)

Horn, H.; Balocchi, A.; Marie, X.; Bakin, A.; Waag, A.; Oestreich, M.; Hübner, J.

2013-01-01

We investigate the intrinsic spin dynamics of electrons bound to Al impurities in bulk ZnO by optical spin noise spectroscopy. Spin noise spectroscopy enables us to investigate the longitudinal and transverse spin relaxation time with respect to nuclear and external magnetic fields in a single spectrum. On one hand, the spin dynamic is dominated by the intrinsic hyperfine interaction with the nuclear spins of the naturally occurring 67Zn isotope. We measure a typical spin dephasing time of 23 ns, in agreement with the expected theoretical values. On the other hand, we measure a third, very high spin dephasing rate which is attributed to a high defect density of the investigated ZnO material. Measurements of the spin dynamics under the influence of transverse as well as longitudinal external magnetic fields unambiguously reveal the intriguing connections of the electron spin with its nuclear and structural environment.

Fingerprints of single nuclear spin energy levels using STM - ENDOR

NASA Astrophysics Data System (ADS)

Manassen, Yishay; Averbukh, Michael; Jbara, Moamen; Siebenhofer, Bernhard; Shnirman, Alexander; Horovitz, Baruch

2018-04-01

We performed STM-ENDOR experiments where the intensity of one of the hyperfine components detected in ESR-STM is recorded while an rf power is irradiated into the tunneling junction and its frequency is swept. When the latter frequency is near a nuclear transition a dip in ESR-STM signal is observed. This experiment was performed in three different systems: near surface SiC vacancies where the electron spin is coupled to a next nearest neighbor 29Si nucleus; Cu deposited on Si(111)7x7 surface, where the unpaired electron of the Cu atom is coupled to the Cu nucleus (63Cu, 65Cu) and on Tempo molecules adsorbed on Au(111), where the unpaired electron is coupled to a Nitrogen nucleus (14N). While some of the hyperfine values are unresolved in the ESR-STM data due to linewidth we find that they are accurately determined in the STM-ENDOR data including those from remote nuclei, which are not detected in the ESR-STM spectrum. Furthermore, STM-ENDOR can measure single nuclear Zeeman frequencies, distinguish between isotopes through their different nuclear magnetic moments and detect quadrupole spectra. We also develop and solve a Bloch type equation for the coupled electron-nuclear system that facilitates interpretation of the data. The improved spectral resolution of STM - ENDOR opens many possibilities for nanometric scale chemical analysis.

Double-quantum homonuclear rotary resonance: Efficient dipolar recovery in magic-angle spinning nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Nielsen, N. C.; Bildsøe, H.; Jakobsen, H. J.; Levitt, M. H.

1994-08-01

We describe an efficient method for the recovery of homonuclear dipole-dipole interactions in magic-angle spinning NMR. Double-quantum homonuclear rotary resonance (2Q-HORROR) is established by fulfilling the condition ωr=2ω1, where ωr is the sample rotation frequency and ω1 is the nutation frequency around an applied resonant radio frequency (rf) field. This resonance can be used for double-quantum filtering and measurement of homonuclear dipolar interactions in the presence of magic-angle spinning. The spin dynamics depend only weakly on crystallite orientation allowing good performance for powder samples. Chemical shift effects are suppressed to zeroth order. The method is demonstrated for singly and doubly 13C labeled L-alanine.

Sensitizing solid state nuclear magnetic resonance of dilute nuclei by spin-diffusion assisted polarization transfers.

PubMed

Lupulescu, Adonis; Frydman, Lucio

2011-10-07

Recent years have witnessed efforts geared at increasing the sensitivity of NMR experiments, by relying on the suitable tailoring and exploitation of relaxation phenomena. These efforts have included the use of paramagnetic agents, enhanced (1)H-(1)H incoherent and coherent transfers processes in 2D liquid state spectroscopy, and homonuclear (13)C-(13)C spin diffusion effects in labeled solids. The present study examines some of the opportunities that could open when exploiting spontaneous (1)H-(1)H spin-diffusion processes, to enhance relaxation and to improve the sensitivity of dilute nuclei in solid state NMR measurements. It is shown that polarization transfer experiments executed under sufficiently fast magic-angle-spinning conditions, enable a selective polarization of the dilute low-γ spins by their immediate neighboring protons. Repolarization of the latter can then occur during the time involved in monitoring the signal emitted by the low-γ nuclei. The basic features involved in the resulting approach, and its potential to improve the effective sensitivity of solid state NMR measurements on dilute nuclei, are analyzed. Experimental tests witness the advantages that could reside from utilizing this kind of approach over conventional cross-polarization processes. These measurements also highlight a number of limitations that will have to be overcome for transforming selective polarization transfers of this kind into analytical methods of choice. © 2011 American Institute of Physics

Instrumentation for cryogenic magic angle spinning dynamic nuclear polarization using 90 L of liquid nitrogen per day

NASA Astrophysics Data System (ADS)

Albert, Brice J.; Pahng, Seong Ho; Alaniva, Nicholas; Sesti, Erika L.; Rand, Peter W.; Saliba, Edward P.; Scott, Faith J.; Choi, Eric J.; Barnes, Alexander B.

2017-10-01

Cryogenic sample temperatures can enhance NMR sensitivity by extending spin relaxation times to improve dynamic nuclear polarization (DNP) and by increasing Boltzmann spin polarization. We have developed an efficient heat exchanger with a liquid nitrogen consumption rate of only 90 L per day to perform magic-angle spinning (MAS) DNP experiments below 85 K. In this heat exchanger implementation, cold exhaust gas from the NMR probe is returned to the outer portion of a counterflow coil within an intermediate cooling stage to improve cooling efficiency of the spinning and variable temperature gases. The heat exchange within the counterflow coil is calculated with computational fluid dynamics to optimize the heat transfer. Experimental results using the novel counterflow heat exchanger demonstrate MAS DNP signal enhancements of 328 ± 3 at 81 ± 2 K, and 276 ± 4 at 105 ± 2 K.

Quantum entanglement analysis of an optically excited coupling of two nuclear spins via a mediator: Combining the quantum concurrence and negativity

NASA Astrophysics Data System (ADS)

Fu, Chenghua; Hu, Zhanning

2018-03-01

In this paper, we investigate the characteristics of the nuclear spin entanglement generated by an intermedium with an optically excited triplet. Significantly, the interaction between the two nuclear spins presents to be a direct XY coupling in each of the effective subspace Hamiltonians which are obtained by applying a transformation on the natural Hamiltonian. The quantum concurrence and negativity are discussed to quantitatively describe the quantum entanglement, and a comparison between them can reveal the nature of their relationship. An innovative general equation describing the relationship between the concurrence and negativity is explicitly obtained.

The direct exchange mechanism of induced spin polarization of low-dimensional π-conjugated carbon- and h-BN fragments at LSMO(001) MnO-terminated interfaces

NASA Astrophysics Data System (ADS)

Kuklin, Artem V.; Kuzubov, Alexander A.; Kovaleva, Evgenia A.; Lee, Hyosun; Sorokin, Pavel B.; Sakai, Seiji; Entani, Shiro; Naramoto, Hiroshi; Avramov, Paul

2017-10-01

Induced spin polarization of π-conjugated carbon and h-BN low dimensional fragments at the interfaces formed by deposition of pentacene molecule and narrow zigzag graphene and h-BN nanoribbons on MnO2-terminated LSMO(001) thin film was studied using GGA PBE+U PAW D3-corrected approach. Induced spin polarization of π-conjugated low-dimensional fragments is caused by direct exchange with Mn ions of LSMO(001) MnO-derived surface. Due to direct exchange, the pentacene molecule changes its diamagnetic narrow-band gap semiconducting nature to the ferromagnetic semiconducting state with 0.15 eV energy shift between spin-up and spin-down valence bands and total magnetic moment of 0.11 μB. Direct exchange converts graphene nanoribbon to 100% spin-polarized half-metal with large amplitude of spin-up electronic density at the Fermi level. The direct exchange narrows the h-BN nanoribbon band gap from 4.04 to 1.72 eV in spin-up channel and converts the h-BN ribbon semiconducting diamagnetic nature to a semiconducting magnetic one. The electronic structure calculations demonstrate a possibility to control the spin properties of low-dimensional π-conjugated carbon and h-BN fragments by direct exchange with MnO-derived LSMO(001) surface for spin-related applications.

Switching-angle sample spinning NMR probe with a commercially available 20 kHz spinning system

NASA Astrophysics Data System (ADS)

Mizuno, Takashi; Takegoshi, K.; Terao, Takehiko

2004-11-01

A switching-angle sample spinning (SASS) probe workable at high spinning speeds was developed using a commercially available rotor/housing system. Details of the construction are described. As application examples of the SASS probe, we report experiments of powder pattern separation at the spinning speed of 20 kHz and broadband 13C- 13C polarization transfer at 16 kHz.

Fractionated Mercury Isotopes in Fish: The Effects of Nuclear Mass, Spin, and Volume

NASA Astrophysics Data System (ADS)

Das, R.; Odom, A. L.

2007-12-01

, and thus more than one mass-independent isotope effect is inferred. MIF of mercury can be caused by the nuclear volume effect. Schauble, 2007 has calculated nuclear volume fractionation scaling factors for a number of common mercury chemical species in equilibrium with Hg° vapor. From his calculations the nuclear field shift effect is larger in Δ199Hg than in Δ201Hg by approximately a factor of two. The predominant mercury chemical species in fish is methylmercury cysteine. From the experimental studies of Buchachenko and others (2004) on the reaction of methylmercury chloride with creatine kinase it seems reasonable to predicted that the thiol functional groups of cysteine gets enriched in 199Hg and 201Hg. Here the magnetic isotope effect (MIE) produces a kinetic partial separation of isotopes with non-zero nuclear spin quantum numbers from the even-N isotopes. The ratio of enrichment of Δ201Hg /Δ199Hg is predicted from theory to be 1.11, which is the ratio of the magnetic moments of 199Hg and 201Hg. Because mercury possesses two odd-N isotopes, it is possible to detect and evaluate the effects of two distinct, mass-independent isotope fractionating processes. From the data obtained on fish samples, we can deconvolute the contributions of the isotope effects of nuclear mass, spin and volume. For these samples the role of spin or the magnetic isotope effect is the most dominant.

Nuclear Spin relaxation mediated by Fermi-edge electrons in n-type GaAs

NASA Astrophysics Data System (ADS)

Kotur, M.; Dzhioev, R. I.; Kavokin, K. V.; Korenev, V. L.; Namozov, B. R.; Pak, P. E.; Kusrayev, Yu. G.

2014-03-01

A method based on the optical orientation technique was developed to measure the nuclear-spin lattice relaxation time T 1 in semiconductors. It was applied to bulk n-type GaAs, where T 1 was measured after switching off the optical excitation in magnetic fields from 400 to 1200 G at low (< 30 K) temperatures. The spin-lattice relaxation of nuclei in the studied sample with n D = 9 × 1016 cm-3 was found to be determined by hyperfine scattering of itinerant electrons (Korringa mechanism) which predicts invariability of T 1 with the change in magnetic field and linear dependence of the relaxation rate on temperature. This result extends the experimentally verified applicability of the Korringa relaxation law in degenerate semiconductors, previously studied in strong magnetic fields (several Tesla), to the moderate field range.

PHOTOCHEMICALLY-INDUCED ALTERATION OF STABLE CARBON ISOTOPE RATIOS (DELTA C-13) IN TERRIGENOUS DISSOLVED ORGANIC CARBON

EPA Science Inventory

Exposure of riverine waters to natural sunlight initiated alterations in stable carbon isotope ratios (delta C-13) of the associated dissolved organic carbon (DOC). Water samples were collected from two compositionally distinct coastal river systems in the southeastern United Sta...

Accelerating the spin-up of the coupled carbon and nitrogen cycle model in CLM4

DOE PAGES

Fang, Yilin; Liu, Chongxuan; Leung, Lai-Yung R.

2015-03-24

The commonly adopted biogeochemistry spin-up process in an Earth system model (ESM) is to run the model for hundreds to thousands of years subject to periodic atmospheric forcing to reach dynamic steady state of the carbon–nitrogen (CN) models. A variety of approaches have been proposed to reduce the computation time of the spin-up process. Significant improvement in computational efficiency has been made recently. However, a long simulation time is still required to reach the common convergence criteria of the coupled carbon–nitrogen model. A gradient projection method was proposed and used to further reduce the computation time after examining the trendmore » of the dominant carbon pools. The Community Land Model version 4 (CLM4) with a carbon and nitrogen component was used in this study. From point-scale simulations, we found that the method can reduce the computation time by 20–69% compared to one of the fastest approaches in the literature. We also found that the cyclic stability of total carbon for some cases differs from that of the periodic atmospheric forcing, and some cases even showed instability. Close examination showed that one case has a carbon periodicity much longer than that of the atmospheric forcing due to the annual fire disturbance that is longer than half a year. The rest was caused by the instability of water table calculation in the hydrology model of CLM4. The instability issue is resolved after we replaced the hydrology scheme in CLM4 with a flow model for variably saturated porous media.« less

Extreme (13)C depletion of carbonates formed during oxidation of biogenic methane in fractured granite.

PubMed

Drake, Henrik; Åström, Mats E; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

2015-05-07

Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as -69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to -125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane.

Frequency-selective REDOR and spin-diffusion relays in uniformly labeled whole cells.

PubMed

Rice, David M; Romaniuk, Joseph A H; Cegelski, Lynette

2015-11-01

Solid-state NMR is a powerful and non-perturbative method to measure and define chemical composition and architecture in bacterial cell walls, even in the context of whole cells. Most NMR studies on whole cells have used selectively labeled samples. Here, we introduce an NMR sequence relay using frequency-selective REDOR (fsREDOR) and spin diffusion elements to probe a unique amine contribution in uniformly (13)C- and (15)N-labeled Staphylococcus aureus whole cells that we attribute to the d-alanine of teichoic acid. In addition to the primary peptidoglycan structural scaffold, cell walls can contain significant amounts of teichoic acid that contribute to cell-wall function. When incorporated into teichoic acid, d-alanine is present as an ester, connected via its carbonyl to a ribitol carbon, and thus has a free amine. Teichoic acid d-Ala is removed during cell-wall isolations and can only be detected in the context of whole cells. The sequence presented here begins with fsREDOR and a chemical shift evolution period for 2D data acquisition, followed by DARR spin diffusion and then an additional fsREDOR period. fsREDOR elements were used for (13)C observation to avoid complications from (13)C-(13)C couplings due to uniform labeling and for (15)N dephasing to achieve selectivity in the nitrogens serving as dephasers. The results show that the selected amine nitrogen of interest is near to teichoic acid ribitol carbons and also the methyl group carbon associated with alanine. In addition, its carbonyl is not significantly dephased by amide nitrogens, consistent with the expected microenvironment around teichoic acid. Copyright © 2015 Elsevier Inc. All rights reserved.

Accounting for disturbance history in models: using remote sensing to constrain carbon and nitrogen pool spin-up.

PubMed

Hanan, Erin J; Tague, Christina; Choate, Janet; Liu, Mingliang; Kolden, Crystal; Adam, Jennifer

2018-03-24

Disturbances such as wildfire, insect outbreaks, and forest clearing, play an important role in regulating carbon, nitrogen, and hydrologic fluxes in terrestrial watersheds. Evaluating how watersheds respond to disturbance requires understanding mechanisms that interact over multiple spatial and temporal scales. Simulation modeling is a powerful tool for bridging these scales; however, model projections are limited by uncertainties in the initial state of plant carbon and nitrogen stores. Watershed models typically use one of two methods to initialize these stores: spin-up to steady state or remote sensing with allometric relationships. Spin-up involves running a model until vegetation reaches equilibrium based on climate. This approach assumes that vegetation across the watershed has reached maturity and is of uniform age, which fails to account for landscape heterogeneity and non-steady-state conditions. By contrast, remote sensing, can provide data for initializing such conditions. However, methods for assimilating remote sensing into model simulations can also be problematic. They often rely on empirical allometric relationships between a single vegetation variable and modeled carbon and nitrogen stores. Because allometric relationships are species- and region-specific, they do not account for the effects of local resource limitation, which can influence carbon allocation (to leaves, stems, roots, etc.). To address this problem, we developed a new initialization approach using the catchment-scale ecohydrologic model RHESSys. The new approach merges the mechanistic stability of spin-up with the spatial fidelity of remote sensing. It uses remote sensing to define spatially explicit targets for one or several vegetation state variables, such as leaf area index, across a watershed. The model then simulates the growth of carbon and nitrogen stores until the defined targets are met for all locations. We evaluated this approach in a mixed pine-dominated watershed in

Relativistic Zeroth-Order Regular Approximation Combined with Nonhybrid and Hybrid Density Functional Theory: Performance for NMR Indirect Nuclear Spin-Spin Coupling in Heavy Metal Compounds.

PubMed

Moncho, Salvador; Autschbach, Jochen

2010-01-12

A benchmark study for relativistic density functional calculations of NMR spin-spin coupling constants has been performed. The test set contained 47 complexes with heavy metal atoms (W, Pt, Hg, Tl, Pb) with a total of 88 coupling constants involving one or two heavy metal atoms. One-, two-, three-, and four-bond spin-spin couplings have been computed at different levels of theory (nonhybrid vs hybrid DFT, scalar vs two-component relativistic). The computational model was based on geometries fully optimized at the BP/TZP scalar relativistic zeroth-order regular approximation (ZORA) and the conductor-like screening model (COSMO) to include solvent effects. The NMR computations also employed the continuum solvent model. Computations in the gas phase were performed in order to assess the importance of the solvation model. The relative median deviations between various computational models and experiment were found to range between 13% and 21%, with the highest-level computational model (hybrid density functional computations including scalar plus spin-orbit relativistic effects, the COSMO solvent model, and a Gaussian finite-nucleus model) performing best.

Measuring the Spin Correlation of Nuclear Muon Capture in HELIUM-3.

NASA Astrophysics Data System (ADS)

McCracken, Dorothy Jill

1996-06-01

We have completed the first measurement of the spin correlation of nuclear muon capture in ^3 He: mu^- + ^3He to nu _{mu} + ^3 H. From this spin correlation, we can extract the induced pseudoscalar form factor, F_{ rm p}, of the weak charged nuclear current. This form factor is not well known experimentally. If nuclear muon capture were a purely leptonic weak interaction, the current would have no pseudoscalar coupling, and therefore F_{rm p} arises from QCD contributions. Since ^3He is a fairly well understood system, a precise measurement of F_{rm p} could provide a direct test of the theories which describe QCD at low energies. This experiment was performed at TRIUMF in Vancouver, BC, using a muon beam. We stopped unpolarized muons in a laser polarized target filled with ^3 He and Rb vapor. The muons were captured into atomic orbitals, forming muonic ^3He which was then polarized via collisions with the optically pumped Rb vapor. When polarized muons undergo nuclear capture in ^3He, the total capture rate is proportional to (1 + {rm A_ {v}P_{v}cos} theta) where theta is the angle between the muon polarization and the triton recoil direction, P_{rm v} is the muon vector polarization and A_ {rm v} is the vector analyzing power. The partially conserved axial current hypothesis (PCAC) predicts that A_{rm v} = 0.524 +/- 0.006 Our measurement of A_{rm v} is in agreement with this prediction: A_{rm v } = 0.604 +/- 0.093 (stat.) _sp{-.142}{+.112}(syst.). This thesis will describe the design, construction, and operation of the device which simultaneously served as a polarized target and a gridded ion chamber. The ion chamber apparatus enabled us to identify recoil tritons as well as determine their direction of motion. The directional information was obtained by fitting the shapes of the pulses generated by the tritons. In addition, this thesis will describe in detail the analysis of these pulses which resulted in a measurement of the raw forward/backward asymmetry of

Carbon decorative coatings by dip-, spin-, and spray-assisted layer-by-layer assembly deposition.

PubMed

Hong, Jinkee; Kang, Sang Wook

2011-09-01

We performed a comparative surface analysis of all-carbon nano-objects (multiwall carbon nanotubes (MWNT) or graphene oxide (GO) sheets) based multilayer coatings prepared using three widely used nanofilm fabrication methods: dip-, spin-, and spray-assisted layer-by-layer (LbL) deposition. The resultant films showed a marked difference in their growth mechanisms and surface morphologies. Various carbon decorative coatings were synthesized with different surface roughness values, despite identical preparation conditions. In particular, smooth to highly rough all-carbon surfaces, as determined by atomic force microscopy (AFM) and scanning electron microscopy (SEM), were readily obtained by manipulating the LbL deposition methods. As was confirmed by the AFM and SEM analyses, this finding indicated the fundamental morphological evolution of one-dimensional nano-objects (MWNT) and two-dimensional nano-objects (GO) by control of the surface roughness through the deposition method. Therefore, an analysis of the three LbL-assembly methods presented herein may offer useful information about the industrial use of carbon decorative coatings and provide an insight into ways to control the structures of multilayer coatings by tuning the morphologies of carbon nano-objects.

NMR Spin-Lock Induced Crossing (SLIC) Dispersion and Long-Lived Spin States of Gaseous Propane at Low Magnetic Field (0.05 T)

PubMed Central

Barskiy, Danila A.; Salnikov, Oleg G.; Romanov, Alexey S.; Feldman, Matthew A.; Coffey, Aaron M.; Kovtunov, Kirill V.; Koptyug, Igor V.; Chekmenev, Eduard Y.

2017-01-01

When parahydrogen reacts with propylene in low magnetic fields (e.g., 0.05 T), the reaction product propane develops an overpopulation of pseudo-singlet nuclear spin states. We studied how the spin-lock induced crossing (SLIC) technique can be used to convert these pseudo-singlet spin states of hyperpolarized gaseous propane into observable magnetization and to detect 1H NMR signal directly at 0.05 T. The theoretical simulation and experimental study of the NMR signal dependence on B1 power (SLIC amplitude) exhibits a well-resolved dispersion, which is induced by the spin-spin couplings in the eight-proton spin system of propane. We also measured the exponential decay time constants (TLLSS or TS) of these pseudo-singlet long-lived spin states (LLSS) by varying the time between hyperpolarized propane production and SLIC detection. We have found that, on average, TS is approximately 3 times longer than the corresponding T1 value under the same conditions in the range of pressures studied (up to 7.6 atm). Moreover, TS may exceed 13 seconds at pressures above 7 atm in the gas phase. These results are in agreement with the previous reports, and they corroborate a great potential of long-lived hyperpolarized propane as an inhalable gaseous contrast agent for lung imaging and as a molecular tracer to study porous media using low-field NMR and MRI. PMID:28152435

NMR Spin-Lock Induced Crossing (SLIC) dispersion and long-lived spin states of gaseous propane at low magnetic field (0.05 T)

NASA Astrophysics Data System (ADS)

Barskiy, Danila A.; Salnikov, Oleg G.; Romanov, Alexey S.; Feldman, Matthew A.; Coffey, Aaron M.; Kovtunov, Kirill V.; Koptyug, Igor V.; Chekmenev, Eduard Y.

2017-03-01

When parahydrogen reacts with propylene in low magnetic fields (e.g., 0.05 T), the reaction product propane develops an overpopulation of pseudo-singlet nuclear spin states. We studied how the Spin-Lock Induced Crossing (SLIC) technique can be used to convert these pseudo-singlet spin states of hyperpolarized gaseous propane into observable magnetization and to detect 1H NMR signal directly at 0.05 T. The theoretical simulation and experimental study of the NMR signal dependence on B1 power (SLIC amplitude) exhibits a well-resolved dispersion, which is induced by the spin-spin couplings in the eight-proton spin system of propane. We also measured the exponential decay time constants (TLLSS or TS) of these pseudo-singlet long-lived spin states (LLSS) by varying the time between hyperpolarized propane production and SLIC detection. We have found that, on average, TS is approximately 3 times longer than the corresponding T1 value under the same conditions in the range of pressures studied (up to 7.6 atm). Moreover, TS may exceed 13 s at pressures above 7 atm in the gas phase. These results are in agreement with the previous reports, and they corroborate a great potential of long-lived hyperpolarized propane as an inhalable gaseous contrast agent for lung imaging and as a molecular tracer to study porous media using low-field NMR and MRI.

Relativistic theory of nuclear spin-rotation tensor with kinetically balanced rotational London orbitals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Yunlong; Zhang, Yong; Liu, Wenjian, E-mail: liuwjbdf@gmail.com

2014-10-28

Both kinetically balanced (KB) and kinetically unbalanced (KU) rotational London orbitals (RLO) are proposed to resolve the slow basis set convergence in relativistic calculations of nuclear spin-rotation (NSR) coupling tensors of molecules containing heavy elements [Y. Xiao and W. Liu, J. Chem. Phys. 138, 134104 (2013)]. While they perform rather similarly, the KB-RLO Ansatz is clearly preferred as it ensures the correct nonrelativistic limit even with a finite basis. Moreover, it gives rise to the same “direct relativistic mapping” between nuclear magnetic resonance shielding and NSR coupling tensors as that without using the London orbitals [Y. Xiao, Y. Zhang, andmore » W. Liu, J. Chem. Theory Comput. 10, 600 (2014)].« less

Nuclear Magnetic Resonance Shift Reagents: Abnormal 13C Shifts Produced by Complexation of Lanthanide Chelates with Saturated Amines and n-Butyl Isocyanide

PubMed Central

Marzin, Claude; Leibfritz, Dieter; Hawkes, Geoffrey E.; Roberts, John D.

1973-01-01

Lanthanide-induced shfits of 13C nuclear magnetic resonances are reported for several amines and n-butyl isocyanide. Contact contributions to such shifts, especially of β carbons, are clearly important for the chelates of Eu+3 and Pr+3. The importance of contact terms is shown to change in a rather predictable manner with the structure of the amine. PMID:16592062

Role of chiral quantum Hall edge states in nuclear spin polarization.

PubMed

Yang, Kaifeng; Nagase, Katsumi; Hirayama, Yoshiro; Mishima, Tetsuya D; Santos, Michael B; Liu, Hongwu

2017-04-20

Resistively detected NMR (RDNMR) based on dynamic nuclear polarization (DNP) in a quantum Hall ferromagnet (QHF) is a highly sensitive method for the discovery of fascinating quantum Hall phases; however, the mechanism of this DNP and, in particular, the role of quantum Hall edge states in it are unclear. Here we demonstrate the important but previously unrecognized effect of chiral edge modes on the nuclear spin polarization. A side-by-side comparison of the RDNMR signals from Hall bar and Corbino disk configurations allows us to distinguish the contributions of bulk and edge states to DNP in QHF. The unidirectional current flow along chiral edge states makes the polarization robust to thermal fluctuations at high temperatures and makes it possible to observe a reciprocity principle of the RDNMR response. These findings help us better understand complex NMR responses in QHF, which has important implications for the development of RDNMR techniques.

Anisotropic Rotational Diffusion Studied by Nuclear Spin Relaxation and Molecular Dynamics Simulation: An Undergraduate Physical Chemistry Laboratory

ERIC Educational Resources Information Center

Fuson, Michael M.

2017-01-01

Laboratories studying the anisotropic rotational diffusion of bromobenzene using nuclear spin relaxation and molecular dynamics simulations are described. For many undergraduates, visualizing molecular motion is challenging. Undergraduates rarely encounter laboratories that directly assess molecular motion, and so the concept remains an…

Spontaneous 15N Nuclear Spin Hyperpolarization in Metal-Free Activation of Parahydrogen by Molecular Tweezers

PubMed Central

2018-01-01

The ability of frustrated Lewis pairs (FLPs) to activate H2 is of significant interest for metal-free catalysis. The activation of H2 is also the key element of parahydrogen-induced polarization (PHIP), one of the nuclear spin hyperpolarization techniques. It is demonstrated that o-phenylene-based ansa-aminoboranes (AABs) can produce 1H nuclear spin hyperpolarization through a reversible interaction with parahydrogen at ambient temperatures. Heteronuclei are useful in NMR and MRI as well because they have a broad chemical shift range and long relaxation times and may act as background-free labels. We report spontaneous formation of 15N hyperpolarization of the N–H site for a family of AABs. The process is efficient at the high magnetic field of an NMR magnet (7 T), and it provides up to 350-fold 15N signal enhancements. Different hyperpolarization effects are observed with various AAB structures and in a broad temperature range. Spontaneous hyperpolarization, albeit an order of magnitude weaker than that for 15N, was also observed for 11B nuclei. PMID:29401399

Magnetic Susceptibility and Spin Exchange Interactions of the Hexagonal Perovskite-Type Oxides Sr 4/3(Mn 2/3Ni 1/3)O 3

NASA Astrophysics Data System (ADS)

El Abed, A.; Gaudin, E.; Darriet, J.; Whangbo, M.-H.

2002-02-01

Magnetic susceptibility measurements were carried out for two hexagonal perovskite-type oxides Sr1+x(Mn1-xNix)O3 with slightly different compositions (i.e., x={1}/{3} and 0.324). A significant difference in the susceptibilities of the two phases demonstrates the need to control phase compositions accurately. Sr4/3(Mn2/3Ni1/3)O3 consists of two spin sublattices, i.e., the Mn4+ and the Ni2+ ion sublattices. Spin dimer analysis was carried out to examine the relative strengths in the spin exchange interactions of the Mn4+ ion sublattice. The temperature dependence of the magnetic susceptibility of Sr4/3(Mn2/3Ni1/3)O3 was found consistent with a picture in which the Mn4+ ion sublattice has weakly interacting antiferromagnetically coupled (Mn4+)2 dimers, the Ni2+ ion sublattice acts as a paramagnetic system, and the two sublattices are nearly independent.

Adiabatic quantum computing with spin qubits hosted by molecules.

PubMed

Yamamoto, Satoru; Nakazawa, Shigeaki; Sugisaki, Kenji; Sato, Kazunobu; Toyota, Kazuo; Shiomi, Daisuke; Takui, Takeji

2015-01-28

A molecular spin quantum computer (MSQC) requires electron spin qubits, which pulse-based electron spin/magnetic resonance (ESR/MR) techniques can afford to manipulate for implementing quantum gate operations in open shell molecular entities. Importantly, nuclear spins, which are topologically connected, particularly in organic molecular spin systems, are client qubits, while electron spins play a role of bus qubits. Here, we introduce the implementation for an adiabatic quantum algorithm, suggesting the possible utilization of molecular spins with optimized spin structures for MSQCs. We exemplify the utilization of an adiabatic factorization problem of 21, compared with the corresponding nuclear magnetic resonance (NMR) case. Two molecular spins are selected: one is a molecular spin composed of three exchange-coupled electrons as electron-only qubits and the other an electron-bus qubit with two client nuclear spin qubits. Their electronic spin structures are well characterized in terms of the quantum mechanical behaviour in the spin Hamiltonian. The implementation of adiabatic quantum computing/computation (AQC) has, for the first time, been achieved by establishing ESR/MR pulse sequences for effective spin Hamiltonians in a fully controlled manner of spin manipulation. The conquered pulse sequences have been compared with the NMR experiments and shown much faster CPU times corresponding to the interaction strength between the spins. Significant differences are shown in rotational operations and pulse intervals for ESR/MR operations. As a result, we suggest the advantages and possible utilization of the time-evolution based AQC approach for molecular spin quantum computers and molecular spin quantum simulators underlain by sophisticated ESR/MR pulsed spin technology.

Fingerprints of single nuclear spin energy levels using STM - ENDOR.

PubMed

Manassen, Yishay; Averbukh, Michael; Jbara, Moamen; Siebenhofer, Bernhard; Shnirman, Alexander; Horovitz, Baruch

2018-04-01

We performed STM-ENDOR experiments where the intensity of one of the hyperfine components detected in ESR-STM is recorded while an rf power is irradiated into the tunneling junction and its frequency is swept. When the latter frequency is near a nuclear transition a dip in ESR-STM signal is observed. This experiment was performed in three different systems: near surface SiC vacancies where the electron spin is coupled to a next nearest neighbor 29 Si nucleus; Cu deposited on Si(111)7x7 surface, where the unpaired electron of the Cu atom is coupled to the Cu nucleus ( 63 Cu, 65 Cu) and on Tempo molecules adsorbed on Au(111), where the unpaired electron is coupled to a Nitrogen nucleus ( 14 N). While some of the hyperfine values are unresolved in the ESR-STM data due to linewidth we find that they are accurately determined in the STM-ENDOR data including those from remote nuclei, which are not detected in the ESR-STM spectrum. Furthermore, STM-ENDOR can measure single nuclear Zeeman frequencies, distinguish between isotopes through their different nuclear magnetic moments and detect quadrupole spectra. We also develop and solve a Bloch type equation for the coupled electron-nuclear system that facilitates interpretation of the data. The improved spectral resolution of STM - ENDOR opens many possibilities for nanometric scale chemical analysis. Copyright © 2018 Elsevier Inc. All rights reserved.

Extreme 13C depletion of carbonates formed during oxidation of biogenic methane in fractured granite

PubMed Central

Drake, Henrik; Åström, Mats E.; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

2015-01-01

Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as −69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to −125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane. PMID:25948095

Spin-locking of half-integer quadrupolar nuclei in nuclear magnetic resonance of solids: creation and evolution of coherences.

PubMed

Ashbrook, Sharon E; Wimperis, Stephen

2004-02-08

Spin-locking of half-integer quadrupolar nuclei, such as 23Na (I=3/2) and 27Al (I=5/2), is of renewed interest owing to the development of variants of the multiple-quantum and satellite-transition magic angle spinning (MAS) nuclear magnetic resonance experiments that either utilize spin-locking directly or offer the possibility that spin-locked states may arise. However, the large magnitude and, under MAS, the time dependence of the quadrupolar interaction often result in complex spin-locking phenomena that are not widely understood. Here we show that, following the application of a spin-locking pulse, a variety of coherence transfer processes occur on a time scale of approximately 1/omegaQ before the spin system settles down into a spin-locked state which may itself be time dependent if MAS is performed. We show theoretically for both spin I=3/2 and 5/2 nuclei that the spin-locked state created by this initial rapid dephasing typically consists of a variety of single- and multiple-quantum coherences and nonequilibrium population states and we discuss the subsequent evolution of these under MAS. In contrast to previous work, we consider spin-locking using a wide range of radio frequency field strengths, i.e., a range that covers both the "strong-field" (omega1 > omegaQPAS and "weak-field" (omega1 < omegaQPAS limits. Single- and multiple-quantum filtered spin-locking experiments on NaNO2, NaNO3, and Al(acac)3, under both static and MAS conditions, are used to illustrate and confirm the results of the theoretical discussion.

Parahydrogen-enhanced zero-field nuclear magnetic resonance

NASA Astrophysics Data System (ADS)

Theis, T.; Ganssle, P.; Kervern, G.; Knappe, S.; Kitching, J.; Ledbetter, M. P.; Budker, D.; Pines, A.

2011-07-01

Nuclear magnetic resonance, conventionally detected in magnetic fields of several tesla, is a powerful analytical tool for the determination of molecular identity, structure and function. With the advent of prepolarization methods and detection schemes using atomic magnetometers or superconducting quantum interference devices, interest in NMR in fields comparable to the Earth's magnetic field and below (down to zero field) has been revived. Despite the use of superconducting quantum interference devices or atomic magnetometers, low-field NMR typically suffers from low sensitivity compared with conventional high-field NMR. Here we demonstrate direct detection of zero-field NMR signals generated through parahydrogen-induced polarization, enabling high-resolution NMR without the use of any magnets. The sensitivity is sufficient to observe spectra exhibiting 13C-1H scalar nuclear spin-spin couplings (known as J couplings) in compounds with 13C in natural abundance, without the need for signal averaging. The resulting spectra show distinct features that aid chemical fingerprinting.

Chemistry and palynology of carbon seams and associated rocks from the Witwatersrand goldfields, South Africa

USGS Publications Warehouse

Ebert, L.B.; Robbins, E.I.; Rose, K.D.; Kastrup, R.V.; Scanlon, J.C.; Gebhard, L.A.; Garcia, A.R.

1990-01-01

Carbon seams in the Witwatersrand System of South Africa host some of the richest gold concentrations in the world. A study of the microscopic characteristics in thin sections and acid residues, and of the chemical and physical nature of the carbon-bearing phases, was undertaken to gain some understanding of the biological precursors and thermal changes that have occurred since the seams were buried. The HClHF acid-resistant organic tissues in this Early Proterozoic coal are filamentous and spherical, which are typical morphologies for microorganisms. The tissues are carbonized black as would be expected for metamorphic rocks, so usual palynological techniques were of limited use. Therefore, the chemical and physical nature of the organic remains was studied by H C ratios, X-ray diffraction (XRD), 13C nuclear magnetic resonance (NMR), reductive chemistry, crosspolarization/magic angle spinning NMR (CP/MAS), and electron spin resonance (ESR). The H C ratios of the samples examined are similar to those of semi-anthracite and petroleum cokes from delayed cokers. XRD shows graphite is not present and that the gold is in elemental form, not chemically bound or intercalated between carbon planes. NMR shows that both aromatic and paraffinic carbons are present. Integration of the carbon NMR spectra suggests that 80% of the carbon is sp2-hybridized and 20% is sp3-hybridized. Reductive chemistry shows that the benzenoid entities are larger than common polynuclear aromatic hydrocarbons such as perylene and decacyclene. Dipolar dephasing CP/MAS NMR suggests the presence of two types of paraffinic carbons, a rigid methylene group and a rotating methyl group. The narrowing of the ESR linewidth between room temperature and 300??C shows that the materials examined have not previously been subjected to temperatures as high as 300??C. ?? 1990.

Anomalous electron spin decoherence in an optically pumped quantum dot

NASA Astrophysics Data System (ADS)

Shi, Xiaofeng; Sham, L. J.

2013-03-01

We study the nuclear-spin-fluctuation induced spin decoherence of an electron (SDE) in an optically pumped quantum dot. The SDE is computed in terms of the steady distribution of the nuclear field (SDNF) formed through the hyperfine interaction (HI) with two different nuclear species in the dot. A feedback loop between the optically driven electron spin and the nuclear spin ensemble determines the SDNF [W. Yang and L. J. Sham, Phy. Rev. B 85, 235319(2012)]. Different from that work and others reviewed therein, where a bilinear HI, SαIβ , between the electron (or hole) spin S and the nuclear spin I is used, we use an effective nonlinear interaction of the form SαIβIγ derived from the Fermi-contact HI. Our feedback loop forms a multi-peak SDNF in which the SDE shows remarkable collapses and revivals in nanosecond time scale. Such an anomalous SDE results from a quantum interference effect of the electron Larmor precession in a multi-peak effective magnetic field. In the presence of a bilinear HI that suppresses the nuclear spin fluctuation, the non-Markovian SDE persists whenever there are finite Fermi contact interactions between two or more kinds of nuclei and the electron in the quantum dot. This work is supported by NSF(PHY 1104446) and the US Army Research Office MURI award W911NF0910406.

A high-performance Fortran code to calculate spin- and parity-dependent nuclear level densities

NASA Astrophysics Data System (ADS)

Sen'kov, R. A.; Horoi, M.; Zelevinsky, V. G.

2013-01-01

A high-performance Fortran code is developed to calculate the spin- and parity-dependent shell model nuclear level densities. The algorithm is based on the extension of methods of statistical spectroscopy and implies exact calculation of the first and second Hamiltonian moments for different configurations at fixed spin and parity. The proton-neutron formalism is used. We have applied the method for calculating the level densities for a set of nuclei in the sd-, pf-, and pf+g- model spaces. Examples of the calculations for 28Si (in the sd-model space) and 64Ge (in the pf+g-model space) are presented. To illustrate the power of the method we estimate the ground state energy of 64Ge in the larger model space pf+g, which is not accessible to direct shell model diagonalization due to the prohibitively large dimension, by comparing with the nuclear level densities at low excitation energy calculated in the smaller model space pf. Program summaryProgram title: MM Catalogue identifier: AENM_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AENM_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 193181 No. of bytes in distributed program, including test data, etc.: 1298585 Distribution format: tar.gz Programming language: Fortran 90, MPI. Computer: Any architecture with a Fortran 90 compiler and MPI. Operating system: Linux. RAM: Proportional to the system size, in our examples, up to 75Mb Classification: 17.15. External routines: MPICH2 (http://www.mcs.anl.gov/research/projects/mpich2/) Nature of problem: Calculating of the spin- and parity-dependent nuclear level density. Solution method: The algorithm implies exact calculation of the first and second Hamiltonian moments for different configurations at fixed spin and parity. The code is parallelized using the Message

Solution and Solid State Nuclear Magnetic Resonance Spectroscopic Characterization of Efavirenz.

PubMed

Sousa, Eduardo Gomes Rodrigues de; Carvalho, Erika Martins de; San Gil, Rosane Aguiar da Silva; Santos, Tereza Cristina Dos; Borré, Leandro Bandeira; Santos-Filho, Osvaldo Andrade; Ellena, Javier

2016-09-01

Samples of efavirenz (EFZ) were evaluated to investigate the influence of the micronization process on EFZ stability. A combination of X-ray diffraction, thermal analysis, FTIR, observations of isotropic chemical shifts of (1)H in distinct solvents, their temperature dependence and spin-lattice relaxation time constants (T1), solution (1D and 2D) (13)C nuclear magnetic resonance (NMR), and solid-state (13)C NMR (CPMAS NMR) provides valuable structural information and structural elucidation of micronized EFZ and heptane-recrystallized polymorphs (EFZ/HEPT). This study revealed that the micronization process did not affect the EFZ crystalline structure. It was observed that the structure of EFZ/HEPT is in the same form as that obtained from ethyl acetate/hexane, as shown in the literature. A comparison of the solid-state NMR spectra revealed discrepancies regarding the assignments of some carbons published in the literature that have been resolved. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

High-spin structures in the 139Pr nucleus

NASA Astrophysics Data System (ADS)

Yeoh, E. Y.; Zhu, S. J.; Wang, J. G.; Xiao, Z. G.; Zhang, M.; Yan, W. H.; Wang, R. S.; Xu, Q.; Wu, X. G.; He, C. Y.; Li, G. S.; Zheng, Y.; Li, C. B.; Cao, X. P.; Hu, S. P.; Yao, S. H.; Yu, B. B.

2012-06-01

Background: 139Pr is located in a transitional region of neutron number close to the N=82 shell. The study of its high-spin states and collective bands is important for systematically understanding the nuclear structural characteristics in this region.Purpose: To investigate the high-spin levels and to search for oblate bands in 139Pr.Methods: The high-spin states of 139Pr have been studied via the reaction 124Sn(19F,4n) at a beam energy of 80 MeV. The experiment was carried out at the HI-13 Tandem Accelerator at the China Institute of Atomic Energy (CIAE). The data analysis was done by using the γ-γ coincidence method.Results: The level scheme of 139Pr has been expanded with spin up to 45/2ℏ. A total of 39 new levels and 45 new transitions are identified. Four collective band structures at high-spin states have been newly established. From systematic analysis, one of the bands is proposed as a double decoupled band; two bands are proposed as oblate bands with γ˜-60∘; another band is suggested as an oblate-triaxial band with γ˜-90∘. The other characteristics for these bands are discussed.Conclusions: A new level scheme in 139Pr has been established and the collective bands at high spin have been identified. The result shows that the strong oblate shape-driving effect is caused by neutrons at the high-spin states in 139Pr.

Understanding API-polymer proximities in amorphous stabilized composite drug products using fluorine-carbon 2D HETCOR solid-state NMR.

PubMed

Abraham, Anuji; Crull, George

2014-10-06

A simple and robust method for obtaining fluorine-carbon proximities was established using a (19)F-(13)C heteronuclear correlation (HETCOR) two-dimensional (2D) solid-state nuclear magnetic resonance (ssNMR) experiment under magic-angle spinning (MAS). The method was applied to study a crystalline active pharmaceutical ingredient (API), avagacestat, containing two types of fluorine atoms and its API-polymer composite drug product. These results provide insight into the molecular structure, aid with assigning the carbon resonances, and probe API-polymer proximities in amorphous spray dried dispersions (SDD). This method has an advantage over the commonly used (1)H-(13)C HETCOR because of the large chemical shift dispersion in the fluorine dimension. In the present study, fluorine-carbon distances up to 8 Å were probed, giving insight into the API structure, crystal packing, and assignments. Most importantly, the study demonstrates a method for probing an intimate molecular level contact between an amorphous API and a polymer in an SDD, giving insights into molecular association and understanding of the role of the polymer in API stability (such as recrystallization, degradation, etc.) in such novel composite drug products.

In vivo carbon-13 nuclear magnetic resonance studies of heart metabolism.