Electron spin resonance of an irradiated single crystal of potassium hydrogen maleate

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

Iwasaki, Machio; Itoh, Koichi

1963-09-15

Electron spin resonance absorptions of x-irradiated single crystals of potassium hydrogen maleate and potassium deuterium maleate were observed. Both compounds gave the same hyperfine structures, although the slightly sharper line widths were observed for the deuterium exchanged compound.

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.

Theoretical Studies of the Electron Paramagnetic Resonance Parameters and Local Structure for VO2+ in Oxyfluoroborate Glasses

NASA Astrophysics Data System (ADS)

Zhang, Huaming; Yu, Xiaopeng; Xiao, Wenbo

2017-12-01

The electron paramagnetic resonance parameters (g factors g ‖, g ⊥ and hyperfine structure constants A ‖, A ⊥) of a tetragonal V4+ center in oxyfluoroborate glasses (20Li2O-10Li2F2-70B2O3) are theoretically investigated by using the perturbation formulas for a 3d1 ion in tetragonally compressed octahedra. The calculated results are in good agreement with the experimental data. Local structure parameters of [VO6]8- clusters are obtained from the calculation (i.e., R‖ ≈ 1.74 Å and R⊥ ≈ 1.985 Å for the metal-ligand distances parallel and perpendicular to the C4 axis, respectively). It is shown that the local structure around the V4+ ion possesses a compressed tetragonal distortion along C 4 axis. The signs of the hyperfine structure constants A‖ and A ⊥ for V4+ centers in oxyfluoroborate glasses were also suggested in the discussion.

Hyperfine fields of Fe in Nd2Fe14BandSm2Fe17N3

NASA Astrophysics Data System (ADS)

Akai, Hisazumi; Ogura, Masako

2015-03-01

High saturation magnetization of rare-earth magnets originates from Fe and the strong magnetic anisotropy stems from f-states of rare-earth elements such as Nd and Sm. Therefore the hyperfine fields of both Fe and rare-earth provide us with important pieces of information: Fe NMR enable us to detect site dependence of the local magnetic moment and magnetic anisotropy (Fe sites also contribute to the magnetic anisotropy) while rare-earth NQR directly give the information of electric field gradients (EFG) that are related to the shape of the f-electron cloud as well as the EFG produced by ligands. In this study we focus on the hyperfine fields of materials used as permanent magnets, Nd2Fe14BandSm2Fe17N3 from theoretical points of view. The detailed electronic structure together with the hyperfine interactions are discussed on the basis of the first-principles calculation. In particular, the relations between the observed hyperfine fields and the magnetic properties are studies in detail. The effects of doping of those materials by other elements such as Dy and the effects of N adding in Sm2Fe17N3 will be discussed. This work was supported by Elements Strategy Initiative Center for Magnetic Materials Project, the Ministry of Education, Culture, Sports, Science and Technology, Japan.

Electronic structure and magnetic properties of dilute U impurities in metals

NASA Astrophysics Data System (ADS)

Mohanta, S. K.; Cottenier, S.; Mishra, S. N.

2016-05-01

The electronic structure and magnetic moment of dilute U impurity in metallic hosts have been calculated from first principles. The calculations have been performed within local density approximation of the density functional theory using Augmented plane wave+local orbital (APW+lo) technique, taking account of spin-orbit coupling and Coulomb correlation through LDA+U approach. We present here our results for the local density of states, magnetic moment and hyperfine field calculated for an isolated U impurity embedded in hosts with sp-, d- and f-type conduction electrons. The results of our systematic study provide a comprehensive insight on the pressure dependence of 5f local magnetism in metallic systems. The unpolarized local density of states (LDOS), analyzed within the frame work of Stoner model suggest the occurrence of local moment for U in sp-elements, noble metals and f-block hosts like La, Ce, Lu and Th. In contrast, U is predicted to be nonmagnetic in most transition metal hosts except in Sc, Ti, Y, Zr, and Hf consistent with the results obtained from spin polarized calculation. The spin and orbital magnetic moments of U computed within the frame of LDA+U formalism show a scaling behavior with lattice compression. We have also computed the spin and orbital hyperfine fields and a detail analysis has been carried out. The host dependent trends for the magnetic moment, hyperfine field and 5f occupation reflect pressure induced change of electronic structure with U valency changing from 3+ to 4+ under lattice compression. In addition, we have made a detailed analysis of the impurity induced host spin polarization suggesting qualitatively different roles of f-band electrons on moment stability. The results presented in this work would be helpful towards understanding magnetism and spin fluctuation in U based alloys.

Theoretical hyperfine structures of 19F i and 17O i

NASA Astrophysics Data System (ADS)

Aourir, Nouria; Nemouchi, Messaoud; Godefroid, Michel; Jönsson, Per

2018-03-01

Multiconfiguration Hartree-Fock (MCHF) and multiconfiguration Dirac-Hartree-Fock (MCDHF) calculations are performed for the 2 p5P2o , 2 p4(3P ) 3 s 4P , 2 p4(3P ) 3 s 2P , and 2 p4(3P ) 3 p 4So states of 19F i to determine their hyperfine constants. Several computing strategies are considered to investigate electron correlation and relativistic effects. High-order correlation contributions are included in MCHF calculations based on single and double multireference expansions. The largest components of the single reference MCHF wave functions are selected to define the multireference (MR) sets. In this scheme, relativistic corrections are evaluated in the Breit-Pauli approximation. A similar strategy is used for the calculation of MCDHF relativistic wave functions and hyperfine parameters. While correlation and relativistic corrections are found to be rather small for the ground state, we highlight large relativistic effects on the hyperfine constant A3 /2 of 2 p4(3P ) 3 p 4So and, to a lesser extent, on A1 /2 of 2 p4(3P ) 3 s 4P . As expected for such a light system, electron correlation effects dominate over relativity in the calculation of the hyperfine interaction of all other levels considered. We also revisit the hyperfine constants of 2 p3(4S ) 3 s S5o and 2 p3(4S ) 3 p 5P in 17O using similar strategies. The results are found to be in excellent agreement with experiment.

Hyperfine rather than spin splittings dominate the fine structure of the B (4)Σ(-)-X (4)Σ(-) bands of AlC.

PubMed

Clouthier, Dennis J; Kalume, Aimable

2016-01-21

Laser-induced fluorescence and wavelength resolved emission spectra of the B (4)Σ(-)-X (4)Σ(-) band system of the gas phase cold aluminum carbide free radical have been obtained using the pulsed discharge jet technique. The radical was produced by electron bombardment of a precursor mixture of trimethylaluminum in high pressure argon. High resolution spectra show that each rotational line of the 0-0 and 1-1 bands of AlC is split into at least three components, with very similar splittings and intensities in both the P- and R-branches. The observed structure was reproduced by assuming bβS magnetic hyperfine coupling in the excited state, due to a substantial Fermi contact interaction of the unpaired electron in the aluminum 3s orbital. Rotational analysis has yielded ground and excited state equilibrium bond lengths in good agreement with the literature and our own ab initio values. Small discrepancies in the calculated intensities of the hyperfine lines suggest that the upper state spin-spin constant λ' is of the order of ≈ 0.025-0.030 cm(-1).

Aggregate frequency width, nuclear hyperfine coupling and Jahn-Teller effect of Cu2+ impurity ion ESR in SrLaAlO4 dielectric resonator at 20 millikelvin

NASA Astrophysics Data System (ADS)

Hosain, M. A.; Le Floch, J.-M.; Krupka, J.; Tobar, M. E.

2018-01-01

The impurity paramagnetic ion, Cu2+ substitutes Al in the SrLaAlO4 single crystal lattice, this results in a CuO6 elongated octahedron, and the resulting measured g-factors satisfy four-fold axes variation condition. The aggregate frequency width of the electron spin resonance with the required minimum level of impurity concentration has been evaluated in this single crystal SrLaAlO4 at 20 millikelvin. Measured parallel hyperfine constants, A\\Vert Cu , were determined to be -155.7×10-4~cm-1, ~ -163.0×10-4~cm-1, ~ -178.3×10-4~cm-1 and -211.1×10-4~cm-1 at 9.072~GHz~(WGH4, 1, 1) for the nuclear magnetic quantum number M_I=+\\frac{3}{2}, +\\frac{1}{2}, -\\frac{1}{2} , and -\\frac{3}{2} respectively. The anisotropy of the hyperfine structure reveals the characteristics of the static Jahn-Teller effect. The second-order-anisotropy term, ˜ (\\fracspin{-orbit~coupling}{10D_q}){\\hspace{0pt}}2 , is significant and cannot be disregarded, with the local strain dominating over the observed Zeeman-anisotropy-energy difference. The Bohr electron magneton, β=9.23× 10-24 JT-1 , (within -0.43% so-called experimental error) has been found using the measured spin-Hamiltonian parameters. Measured nuclear dipolar hyperfine structure parameter P\\Vert=12.3×10-4~cm-1 shows that the mean inverse third power of the electron distance from the nucleus is < r-3_q>≃ 5.23 a.u. for Cu2+ ion in the substituted Al3+ ion site assuming nuclear electric quadruple moment Q=-0.211 barn.

HYPERFINE STRUCTURES AND NUCLEAR MOMENTS OF Lu$sup 176$m, Br$sup 80$, Br$sup 80$m, AND I$sup 132$ (thesis)

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

White, M.B.

1962-09-01

The method of atomic-beam radiofrequency spectroscopy was used to determine some nuclear and atomic properties of Lu/sup 176m/, Br/sup 80/, Br/sup 80m/, and I/sup 132/. Hyperfine structure me asurements were raade to determine the magnetic dipole interaction constants and the electric quadrupole interaction constants of all these isotopes. Also the nuclear spin and the electronic g/sub J/ factor were measured for Lu/sup 176m/, and the nuclear magnetic dipole moments and the electric quadrupole moments for the isotopes were calculated. All results are listed. 62 references. (auth)

An ESR study of the stable radical in a γ-irradiated single crystal of 17α-dydroxy-progesterone

NASA Astrophysics Data System (ADS)

Krzyminiewski, R.; Pietrzak, J.; Konopka, R.

1990-11-01

Electron spin resonance spectroscopy was used to investigate γ-radiation damage of 17α-hydroxy-progesterone molecules in a single crystal. Two types of radicals with different rates of recombination were observed and a definite structure was assigned to the specimen by analyzing the orientational variation of the spectra. The unpaired electron of the radical is delocalized in the 2 pz orbitals of the C(6), C(4) and C(3) atoms, giving rise to a hyperfine spectrum by interaction with two equivalent α-protons in positions 4 and 6 and with two non-equivalent β-protons attached to C(7). The hyperfine coupling tensors are reported, together with the g tensor of the radical. The presence of additional intermolecular interactions caused by hydrogen bonding between O(3) and HO(17) of two molecules does not change the type of radical (which is the same as the stable radical in a γ-irradiated single crystal of progesterone) but does increase the hyperfine coupling anisotropy.

Solid-state EPR strategies for the structural characterization of paramagnetic NO adducts of frustrated Lewis pairs (FLPs)

NASA Astrophysics Data System (ADS)

de Oliveira, Marcos; Wiegand, Thomas; Elmer, Lisa-Maria; Sajid, Muhammad; Kehr, Gerald; Erker, Gerhard; Magon, Claudio José; Eckert, Hellmut

2015-03-01

Anisotropic interactions present in three new nitroxide radicals prepared by N,N addition of NO to various borane-phosphane frustrated Lewis pairs (FLPs) have been characterized by continuous-wave (cw) and pulsed X-band EPR spectroscopies in solid FLP-hydroxylamine matrices at 100 K. Anisotropic g-tensor values and 11B, 14N, and 31P hyperfine coupling tensor components have been extracted from continuous-wave lineshape analyses, electron spin echo envelope modulation (ESEEM), and hyperfine sublevel correlation spectroscopy (HYSCORE) experiments with the help of computer simulation techniques. Suitable fitting constraints are developed on the basis of density functional theory (DFT) calculations. These calculations reveal that different from the situation in standard nitroxide radicals (TEMPO), the g-tensors are non-coincident with any of the nuclear hyperfine interaction tensors. The determination of these interaction parameters turns out to be successful, as the cw- and pulse EPR experiments are highly complementary in informational content. While the continuous-wave lineshape is largely influenced by the anisotropic hyperfine coupling to 14N and 31P, the ESEEM and HYSCORE spectra contain important information about the 11B hyperfine coupling and nuclear electric quadrupolar interaction. The set of cw- and pulsed EPR experiments, with fitting constraints developed by DFT calculations, defines an efficient strategy for the structural analysis of paramagnetic FLP adducts.

Solid-state EPR strategies for the structural characterization of paramagnetic NO adducts of frustrated Lewis pairs (FLPs)

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

Oliveira, Marcos de; Magon, Claudio José; Wiegand, Thomas

2015-03-28

Anisotropic interactions present in three new nitroxide radicals prepared by N,N addition of NO to various borane-phosphane frustrated Lewis pairs (FLPs) have been characterized by continuous-wave (cw) and pulsed X-band EPR spectroscopies in solid FLP-hydroxylamine matrices at 100 K. Anisotropic g-tensor values and {sup 11}B, {sup 14}N, and {sup 31}P hyperfine coupling tensor components have been extracted from continuous-wave lineshape analyses, electron spin echo envelope modulation (ESEEM), and hyperfine sublevel correlation spectroscopy (HYSCORE) experiments with the help of computer simulation techniques. Suitable fitting constraints are developed on the basis of density functional theory (DFT) calculations. These calculations reveal that differentmore » from the situation in standard nitroxide radicals (TEMPO), the g-tensors are non-coincident with any of the nuclear hyperfine interaction tensors. The determination of these interaction parameters turns out to be successful, as the cw- and pulse EPR experiments are highly complementary in informational content. While the continuous-wave lineshape is largely influenced by the anisotropic hyperfine coupling to {sup 14}N and {sup 31}P, the ESEEM and HYSCORE spectra contain important information about the {sup 11}B hyperfine coupling and nuclear electric quadrupolar interaction. The set of cw- and pulsed EPR experiments, with fitting constraints developed by DFT calculations, defines an efficient strategy for the structural analysis of paramagnetic FLP adducts.« less

Frequency swept microwaves for hyperfine decoupling and time domain dynamic nuclear polarization

PubMed Central

Hoff, Daniel E.M.; Albert, Brice J.; Saliba, Edward P.; Scott, Faith J.; Choi, Eric J.; Mardini, Michael; Barnes, Alexander B.

2015-01-01

Hyperfine decoupling and pulsed dynamic nuclear polarization (DNP) are promising techniques to improve high field DNP NMR. We explore experimental and theoretical considerations to implement them with magic angle spinning (MAS). Microwave field simulations using the high frequency structural simulator (HFSS) software suite are performed to characterize the inhomogeneous phase independent microwave field throughout a 198 GHz MAS DNP probe. Our calculations show that a microwave power input of 17 W is required to generate an average EPR nutation frequency of 0.84 MHz. We also present a detailed calculation of microwave heating from the HFSS parameters and find that 7.1% of the incident microwave power contributes to dielectric sample heating. Voltage tunable gyrotron oscillators are proposed as a class of frequency agile microwave sources to generate microwave frequency sweeps required for the frequency modulated cross effect, electron spin inversions, and hyperfine decoupling. Electron spin inversions of stable organic radicals are simulated with SPINEVOLUTION using the inhomogeneous microwave fields calculated by HFSS. We calculate an electron spin inversion efficiency of 56% at a spinning frequency of 5 kHz. Finally, we demonstrate gyrotron acceleration potentials required to generate swept microwave frequency profiles for the frequency modulated cross effect and electron spin inversions. PMID:26482131

Frequency swept microwaves for hyperfine decoupling and time domain dynamic nuclear polarization.

PubMed

Hoff, Daniel E M; Albert, Brice J; Saliba, Edward P; Scott, Faith J; Choi, Eric J; Mardini, Michael; Barnes, Alexander B

2015-11-01

Hyperfine decoupling and pulsed dynamic nuclear polarization (DNP) are promising techniques to improve high field DNP NMR. We explore experimental and theoretical considerations to implement them with magic angle spinning (MAS). Microwave field simulations using the high frequency structural simulator (HFSS) software suite are performed to characterize the inhomogeneous phase independent microwave field throughout a 198GHz MAS DNP probe. Our calculations show that a microwave power input of 17W is required to generate an average EPR nutation frequency of 0.84MHz. We also present a detailed calculation of microwave heating from the HFSS parameters and find that 7.1% of the incident microwave power contributes to dielectric sample heating. Voltage tunable gyrotron oscillators are proposed as a class of frequency agile microwave sources to generate microwave frequency sweeps required for the frequency modulated cross effect, electron spin inversions, and hyperfine decoupling. Electron spin inversions of stable organic radicals are simulated with SPINEVOLUTION using the inhomogeneous microwave fields calculated by HFSS. We calculate an electron spin inversion efficiency of 56% at a spinning frequency of 5kHz. Finally, we demonstrate gyrotron acceleration potentials required to generate swept microwave frequency profiles for the frequency modulated cross effect and electron spin inversions. Copyright © 2015 Elsevier Inc. All rights reserved.

High precision hyperfine measurements in Bismuth challenge bound-state strong-field QED

NASA Astrophysics Data System (ADS)

Ullmann, Johannes; Andelkovic, Zoran; Brandau, Carsten; Dax, Andreas; Geithner, Wolfgang; Geppert, Christopher; Gorges, Christian; Hammen, Michael; Hannen, Volker; Kaufmann, Simon; König, Kristian; Litvinov, Yuri A.; Lochmann, Matthias; Maaß, Bernhard; Meisner, Johann; Murböck, Tobias; Sánchez, Rodolfo; Schmidt, Matthias; Schmidt, Stefan; Steck, Markus; Stöhlker, Thomas; Thompson, Richard C.; Trageser, Christian; Vollbrecht, Jonas; Weinheimer, Christian; Nörtershäuser, Wilfried

2017-05-01

Electrons bound in highly charged heavy ions such as hydrogen-like bismuth 209Bi82+ experience electromagnetic fields that are a million times stronger than in light atoms. Measuring the wavelength of light emitted and absorbed by these ions is therefore a sensitive testing ground for quantum electrodynamical (QED) effects and especially the electron-nucleus interaction under such extreme conditions. However, insufficient knowledge of the nuclear structure has prevented a rigorous test of strong-field QED. Here we present a measurement of the so-called specific difference between the hyperfine splittings in hydrogen-like and lithium-like bismuth 209Bi82+,80+ with a precision that is improved by more than an order of magnitude. Even though this quantity is believed to be largely insensitive to nuclear structure and therefore the most decisive test of QED in the strong magnetic field regime, we find a 7-σ discrepancy compared with the theoretical prediction.

High precision hyperfine measurements in Bismuth challenge bound-state strong-field QED.

PubMed

Ullmann, Johannes; Andelkovic, Zoran; Brandau, Carsten; Dax, Andreas; Geithner, Wolfgang; Geppert, Christopher; Gorges, Christian; Hammen, Michael; Hannen, Volker; Kaufmann, Simon; König, Kristian; Litvinov, Yuri A; Lochmann, Matthias; Maaß, Bernhard; Meisner, Johann; Murböck, Tobias; Sánchez, Rodolfo; Schmidt, Matthias; Schmidt, Stefan; Steck, Markus; Stöhlker, Thomas; Thompson, Richard C; Trageser, Christian; Vollbrecht, Jonas; Weinheimer, Christian; Nörtershäuser, Wilfried

2017-05-16

Electrons bound in highly charged heavy ions such as hydrogen-like bismuth 209 Bi 82+ experience electromagnetic fields that are a million times stronger than in light atoms. Measuring the wavelength of light emitted and absorbed by these ions is therefore a sensitive testing ground for quantum electrodynamical (QED) effects and especially the electron-nucleus interaction under such extreme conditions. However, insufficient knowledge of the nuclear structure has prevented a rigorous test of strong-field QED. Here we present a measurement of the so-called specific difference between the hyperfine splittings in hydrogen-like and lithium-like bismuth 209 Bi 82+,80+ with a precision that is improved by more than an order of magnitude. Even though this quantity is believed to be largely insensitive to nuclear structure and therefore the most decisive test of QED in the strong magnetic field regime, we find a 7-σ discrepancy compared with the theoretical prediction.

The pure rotational spectra of the open-shell diatomic molecules PbI and SnI

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

Evans, Corey J., E-mail: cje8@le.ac.uk, E-mail: nick.walker@newcastle.ac.uk; Needham, Lisa-Maria E.; Walker, Nicholas R., E-mail: cje8@le.ac.uk, E-mail: nick.walker@newcastle.ac.uk

2015-12-28

Pure rotational spectra of the ground electronic states of lead monoiodide and tin monoiodide have been measured using a chirped pulsed Fourier transform microwave spectrometer over the 7-18.5 GHz region for the first time. Each of PbI and SnI has a X {sup 2}Π{sub 1/2} ground electronic state and may have a hyperfine structure that aids the determination of the electron electric dipole moment. For each species, pure rotational transitions of a number of different isotopologues and their excited vibrational states have been assigned and fitted. A multi-isotopologue Dunham-type analysis was carried out on both species producing values for Y{submore » 01}, Y{sub 02}, Y{sub 11}, and Y{sub 21}, along with Λ-doubling constants, magnetic hyperfine constants and nuclear quadrupole coupling constants. The Born-Oppenheimer breakdown parameters for Pb have been evaluated and the parameter rationalized in terms of finite nuclear field effects. Analysis of the bond lengths and hyperfine interaction indicates that the bonding in both PbI and SnI is ionic in nature. Equilibrium bond lengths have been evaluated for both species.« less

Hyperfine structure measurements of neutral vanadium by laser-induced fluorescence spectroscopy in the wavelength range from 750 nm to 860 nm

NASA Astrophysics Data System (ADS)

Başar, Gü.; Güzelçimen, F.; Öztürk, I. K.; Er, A.; Bingöl, D.; Kröger, S.; Başar, Gö.

2017-11-01

The hyperfine structure of 57 spectral lines of neutral vanadium has been investigated using a hollow cathode lamp by laser-induced fluorescence spectroscopy in the wavelength range from 750 nm to 860 nm. New magnetic dipole hyperfine structure constants A have been determined for 14 atomic energy levels and new electric quadrupole hyperfine structure constants B for two levels. Additionally previously published hyperfine structure constants A of 56 levels have been measured again. In five cases, the old A values have been rejected and replaced by improved values.

Scanning nuclear resonance imaging of a hyperfine-coupled quantum Hall system.

PubMed

Hashimoto, Katsushi; Tomimatsu, Toru; Sato, Ken; Hirayama, Yoshiro

2018-06-07

Nuclear resonance (NR) is widely used to detect and characterise nuclear spin polarisation and conduction electron spin polarisation coupled by a hyperfine interaction. While the macroscopic aspects of such hyperfine-coupled systems have been addressed in most relevant studies, the essential role of local variation in both types of spin polarisation has been indicated in 2D semiconductor systems. In this study, we apply a recently developed local and highly sensitive NR based on a scanning probe to a hyperfine-coupled quantum Hall (QH) system in a 2D electron gas subject to a strong magnetic field. We succeed in imaging the NR intensity and Knight shift, uncovering the spatial distribution of both the nuclear and electron spin polarisation. The results reveal the microscopic origin of the nonequilibrium QH phenomena, and highlight the potential use of our technique in microscopic studies on various electron spin systems as well as their correlations with nuclear spins.

NMR studies of electronic structure in crystalline and amorphous Zr2PdH/x/

NASA Technical Reports Server (NTRS)

Bowman, R. C., Jr.; Johnson, W. L.; Maeland, A. J.; Rhim, W.-K.

1983-01-01

The proton Knight shifts and spin-lattice relaxation times have been measured in crystalline and amorphous Ze2PdH(x). Core polarization from the Zr d-band dominates the proton hyperfine interactions. The density of Fermi level d-electron states is reduced in the amorphous phase relative to the electron density in crystalline Zr2PdH(x).

Electron paramagnetic resonance of a 10B-containing heterocyclic radical

NASA Astrophysics Data System (ADS)

Eaton, Sandra S.; Ngendahimana, Thacien; Eaton, Gareth R.; Jupp, Andrew R.; Stephan, Douglas W.

2018-05-01

Electron paramagnetic resonance measurements for a 10B-containing heterocyclic phenanthrenedione radical, (C6F5)2B(O2C14H8), were made at X-band in 9:1 toluene:dichloromethane from 10 to 293 K and in toluene from 180 to 293 K. In well-deoxygenated 0.1 mM toluene solution at room temperature hyperfine couplings to 10B, four pairs of protons and five pairs of fluorines contribute to a continuous wave spectrum with many resolved lines. Hyperfine couplings were adjusted to provide the best fit for spectra of the radical enriched in 10B and the analogous radical synthesized with 10,11B in natural abundance, resulting in small refinements of the hyperfine coupling constants previously reported for the natural abundance sample. Electron spin relaxation rates at temperatures between 15 and 293 K were similar for samples containing 10B and natural isotope abundance. Analysis of electron spin echo envelope modulation and hyperfine correlation spectroscopy data at 80 K found Axx = -7.5 ± 0.3, Ayy = -8.5 ± 0.3, and Azz = -10.8 ± 0.3 MHz for 11B, which indicates small spin density on the boron. The spin echo and hyperfine spectroscopy data for the 10B -containing radical are consistent with the factor of 2.99 smaller hyperfine values for 10B than for 11B.

Analysis of structure of hyperfine poly(3-hydroxybutyrate) fibers (PHB) for controlled drug delivery

NASA Astrophysics Data System (ADS)

Olkhov, A. A.; Kosenko, R. Yu; Markin, V. S.; Zykova, A. K.; Pantyukhov, P. V.; Karpova, S. G.; Iordanskii, A. L.

2017-12-01

Hyperfine fibers based on biodegradable poly (3-hydroxybutyrate) with encapsulated drug substance (dipyridamol) were obtained by using electrospinning method. Addition of dipyridamol has a significant effect on geometrical shape and structure of microfibers as well as total porosity of fibrous material. Observation of fibers using scanning electron microscopy (SEM) method showed that without or at lower dipyridamol content (<3%) fibers consisted of interleaved ellipsoid and cylindrical fragments. At higher dipyridamol content (3-5%) anomalous ellipsoid structures did not practically form, and fiber’s shape became cylindrical. The totality of morphological and structural characteristics determined the rate of dipyridamol diffusive transports. The simplified model of drug desorption from fibrous matrix was presented. In current work it was showed that the rate-limiting stage of transport was the diffusion of dipyridamol in the bulk of cylindrical fibers.

Spectroscopy of a Synthetic Trapped Ion Qubit

NASA Astrophysics Data System (ADS)

Hucul, David; Christensen, Justin E.; Hudson, Eric R.; Campbell, Wesley C.

2017-09-01

133Ba+ has been identified as an attractive ion for quantum information processing due to the unique combination of its spin-1 /2 nucleus and visible wavelength electronic transitions. Using a microgram source of radioactive material, we trap and laser cool the synthetic A =133 radioisotope of barium II in a radio-frequency ion trap. Using the same, single trapped atom, we measure the isotope shifts and hyperfine structure of the 62P1 /2↔62S1 /2 and 62P1 /2↔52D3 /2 electronic transitions that are needed for laser cooling, state preparation, and state detection of the clock-state hyperfine and optical qubits. We also report the 62P1 /2↔52D3 /2 electronic transition isotope shift for the rare A =130 and 132 barium nuclides, completing the spectroscopic characterization necessary for laser cooling all long-lived barium II isotopes.

Comparative analysis of the heme iron electronic structure and stereochemistry in tetrameric rabbit hemoglobin and monomeric soybean leghemoglobin a using Mössbauer spectroscopy with a high velocity resolution

NASA Astrophysics Data System (ADS)

Alenkina, I. V.; Kumar, A.; Berkovsky, A. L.; Oshtrakh, M. I.

2018-02-01

A comparative study of tetrameric rabbit hemoglobin and monomeric soybean leghemoglobin a in the oxy- and deoxy-forms was carried out using 57Fe Mössbauer spectroscopy with a high velocity resolution in order to analyze the heme iron electronic structure and stereochemistry in relation to the Mössbauer hyperfine parameters. The Mössbauer spectra of tetrameric rabbit hemoglobin in both forms were fitted using two quadrupole doublets related to the 57Fe in ɑ- and β-subunits. In contrast, the Mössbauer spectra of monomeric soybean leghemoglobin a were fitted using: (i) two quadrupole doublets for the oxy-form related to two conformational states of the distal His E7 imidazole ring and different hydrogen bonding of oxygen molecule in the oxy-form and (ii) using three quadrupole doublets for deoxy-form related to three conformational states of the proximal His F8 imidazole ring. Small variations of Mössbauer hyperfine parameters related to small differences in the heme iron electronic structure and stereochemistry in tetrameric rabbit hemoglobin and monomeric soybean leghemoglobin a are discussed.

Velocity modulation spectroscopy of molecular ions II: The millimeter/submillimeter-wave spectrum of TiF + ( X3Φr)

NASA Astrophysics Data System (ADS)

Halfen, D. T.; Ziurys, L. M.

2006-11-01

The pure rotational spectrum of the molecular ion TiF + in its 3Φr ground state has been measured in the range 327-542 GHz using millimeter-wave direct absorption techniques combined with velocity modulation spectroscopy. TiF + was made in an AC discharge from a mixture of TiCl 4, F 2 in He, and argon. Ten transitions of this ion were recorded. In every transition, fluorine hyperfine interactions, as well as the fine structure splittings, were resolved. The fine structure pattern was found to be regular with almost equal spacing in frequency between the three spin components, in contrast to TiCl +, which is perturbed in the ground state. The data were fit with a case ( a) Hamiltonian and rotational, fine structure, and hyperfine constants were determined. The bond length established for TiF +, r0 = 1.7775 Å, was found to be shorter than that of TiF, r0 = 1.8342 Å—also established from mm-wave data. The hyperfine parameters determined are consistent with a δ1π1 electron configuration with the electrons primarily located on the titanium nucleus. The nuclear spin-orbit constant a indicates that the unpaired electrons are closer to the fluorine nucleus in TiF + relative to TiF, as expected with the decrease in bond length for the ion. The shorter bond distance is thought to arise from increased charge on the titanium nucleus as a result of a Ti 2+F - configuration. A similar decrease in bond length was found for TiCl + relative to TiCl.

A portable version of the program of nettar and villafranca for the simulation of electron paramagnetic resonance spectra of powders

NASA Astrophysics Data System (ADS)

Soulié, Edgar; Gaugenot, Jacques

1995-04-01

Nettar and Villafranca wrote in the FORTRAN programming language a computer program which simulates the electron paramagnetic resonance (EPR) spectra of powders (Journal of Magnetic Resonance, vol. 64 (1985) pp. 61-65). The spin Hamiltonian which their program can handle includes the Zeeman electronic interaction, the fine interaction up to the sixth order in the electron spin, a general hyperfine interaction, an isotropic nuclear Zeeman term; anisotropic ligand hyperfine terms are treated to first order in perturbation. The above Hamiltonian, without the ligand hyperfine terms, is treated exactly, i.e. the resonance equation for a transition between states labeled i and j is solved numerically: h.ν=Ei(H)-Ej(H).

Hyperfine excitation of OH+ by H

NASA Astrophysics Data System (ADS)

Lique, François; Bulut, Niyazi; Roncero, Octavio

2016-10-01

The OH+ ions are widespread in the interstellar medium and play an important role in the interstellar chemistry as they act as precursors to the H2O molecule. Accurate determination of their abundance rely on their collisional rate coefficients with atomic hydrogen and electrons. In this paper, we derive OH+-H fine and hyperfine-resolved rate coefficients by extrapolating recent quantum wave packet calculations for the OH+ + H collisions, including inelastic and exchange processes. The extrapolation method used is based on the infinite order sudden approach. State-to-state rate coefficients between the first 22 fine levels and 43 hyperfine levels of OH+ were obtained for temperatures ranging from 10 to 1000 K. Fine structure-resolved rate coefficients present a strong propensity rule in favour of Δj = ΔN transitions. The Δj = ΔF propensity rule is observed for the hyperfine transitions. The new rate coefficients will help significantly in the interpretation of OH+ spectra from photon-dominated region (PDR), and enable the OH+ molecule to become a powerful astrophysical tool for studying the oxygen chemistry.

Electron-Nuclear Quantum Information Processing

DTIC Science & Technology

2008-11-13

quantum information processing that exploits the anisotropic hyperfine coupling. This scheme enables universal control over a 1-electron, N-nuclear spin...exploits the anisotropic hyperfine coupling. This scheme enables universal control over a 1-electron, N-nuclear spin system, addressing only a...sample of irradiated malonic acid. (a) Papers published in peer-reviewed journals (N/A for none) Universal control of nuclear spins via anisotropic

Structural and magnetic properties of FeCoC system obtained by mechanical alloying

NASA Astrophysics Data System (ADS)

Rincón Soler, A. I.; Rodríguez Jacobo, R. R.; Medina Barreto, M. H.; Cruz-Muñoz, B.

2017-11-01

Fe96-XCoXC4 (x = 0, 10, 20, 30, 40 at. %) alloys were obtained by mechanical alloying of Fe, C and Co powders using high-energy milling. The structural and magnetic properties of the alloy system were analyzed by X-ray diffraction, Scanning Electron Microscopy (SEM), Vibrating Sample Magnetometer (VSM) and Mössbauer Spectrometry at room temperature. The X-ray diffraction patterns showed a BCC-FeCoC structure phase for all samples, as well as a lattice parameter that slightly decreases with Co content. The saturation magnetization and coercive field were analyzed as a function of Co content. The Mössbauer spectra were fitted with a hyperfine magnetic field distribution showing the ferromagnetic behavior and the disordered character of the samples. The mean hyperfine magnetic field remained nearly constant (358 T) with Co content.

Gd(III) complexes as paramagnetic tags: Evaluation of the spin delocalization over the nuclei of the ligand

NASA Astrophysics Data System (ADS)

Collauto, A.; Feintuch, A.; Qi, M.; Godt, A.; Meade, T.; Goldfarb, D.

2016-02-01

Complexes of the Gd(III) ion are currently being established as spin labels for distance determination in biomolecules by pulse dipolar spectroscopy. Because Gd(III) is an f ion, one expects electron spin density to be localized on the Gd(III) ion - an important feature for the mentioned application. Most of the complex ligands have nitrogens as Gd(III) coordinating atoms. Therefore, measurement of the 14N hyperfine coupling gives access to information on the localization of the electron spin on the Gd(III) ion. We carried out W-band, 1D and 2D 14N and 1H ENDOR measurements on the Gd(III) complexes Gd-DOTA, Gd-538, Gd-595, and Gd-PyMTA that serve as spin labels for Gd-Gd distance measurements. The obtained 14N spectra are particularly well resolved, revealing both the hyperfine and nuclear quadrupole splittings, which were assigned using 2D Mims ENDOR experiments. Additionally, the spectral contributions of the two different types of nitrogen atoms of Gd-PyMTA, the aliphatic N atom and the pyridine N atom, were distinguishable. The 14N hyperfine interaction was found to have a very small isotropic hyperfine component of -0.25 to -0.37 MHz. Furthermore, the anisotropic hyperfine interactions with the 14N nuclei and with the non-exchangeable protons of the ligands are well described by the point-dipole approximation using distances derived from the crystal structures. We therefore conclude that the spin density is fully localized on the Gd(III) ion and that the spin density distribution over the nuclei of the ligands is rightfully ignored when analyzing distance measurements.

Nagaoka's atomic model and hyperfine interactions.

PubMed

Inamura, Takashi T

2016-01-01

The prevailing view of Nagaoka's "Saturnian" atom is so misleading that today many people have an erroneous picture of Nagaoka's vision. They believe it to be a system involving a 'giant core' with electrons circulating just outside. Actually, though, in view of the Coulomb potential related to the atomic nucleus, Nagaoka's model is exactly the same as Rutherford's. This is true of the Bohr atom, too. To give proper credit, Nagaoka should be remembered together with Rutherford and Bohr in the history of the atomic model. It is also pointed out that Nagaoka was a pioneer of understanding hyperfine interactions in order to study nuclear structure.

Zeeman-hyperfine structures and isotope effect in the spectrum of Tl I

NASA Astrophysics Data System (ADS)

Bouazza, Safa; Sobolewski, Łukasz Marek; Kwela, Jerzy

2018-01-01

The Zeeman structures of seventeen lines of 205Tl I (Z = 81) covering the UV-NIR spectral range (351.92-1151.28) nm were investigated. Landé gJ-factors for eighteen levels were determined for the first time. Furthermore, we have performed fine structure studies for both even- and odd-configuration levels and determined the relevant parameters. For the 6 s 6p2 configuration we have refined the suggested level energies and predicted positions for missing levels. With regard to hyperfine structure (hfs), we have justified the surprisingly huge value of the magnetic hfs constant A(6s2 10 s) . Moreover, we have extracted the single-electron hfs constant parameter values for the lowest even-parity configurations of 205Tl I; for instance a10s10 (6s2 10 s) = 1015(9) MHz and a6s10 (6 s 6p2) = 217306(205) MHz. Regarding isotope shift analysis we have observed that Dirac-Fock calculations, preferably chosen to take into account the contribution of the p1/2 contact-electron, are in good agreement with experimental data for low-lying levels of each configuration under study.

Measurement of a heavy-hole hyperfine interaction in InGaAs quantum dots using resonance fluorescence.

PubMed

Fallahi, P; Yilmaz, S T; Imamoğlu, A

2010-12-17

We measure the strength and the sign of hyperfine interaction of a heavy hole with nuclear spins in single self-assembled quantum dots. Our experiments utilize the locking of a quantum dot resonance to an incident laser frequency to generate nuclear spin polarization. By monitoring the resulting Overhauser shift of optical transitions that are split either by electron or exciton Zeeman energy with respect to the locked transition using resonance fluorescence, we find that the ratio of the heavy-hole and electron hyperfine interactions is -0.09 ± 0.02 in three quantum dots. Since hyperfine interactions constitute the principal decoherence source for spin qubits, we expect our results to be important for efforts aimed at using heavy-hole spins in quantum information processing.

Sub-Doppler infrared spectroscopy of propargyl radical (H{sub 2}CCCH) in a slit supersonic expansion

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

Chang, Chih-Hsuan; Nesbitt, David J.

The acetylenic CH stretch mode (ν{sub 1}) of propargyl (H{sub 2}CCCH) radical has been studied at sub-Doppler resolution (∼60 MHz) via infrared laser absorption spectroscopy in a supersonic slit-jet discharge expansion, where low rotational temperatures (T{sub rot} = 13.5(4) K) and lack of spectral congestion permit improved determination of band origin and rotational constants for the excited state. For the lowest J states primarily populated in the slit jet cooled expansion, fine structure due to the unpaired electron spin is resolved completely, which permits accurate analysis of electron spin-rotation interactions in the vibrationally excited states (ε{sub aa} = − 518.1(1.8),more » ε{sub bb} = − 13.0(3), ε{sub cc} = − 1.8(3) MHz). In addition, hyperfine broadening in substantial excess of the sub-Doppler experimental linewidths is observed due to nuclear spin–electron spin contributions at the methylenic (—CH{sub 2}) and acetylenic (—CH) positions, which permits detailed modeling of the fine/hyperfine structure line contours. The results are consistent with a delocalized radical spin density extending over both methylenic and acetylenic C atoms, in excellent agreement with simple resonance structures as well as ab initio theoretical calculations.« less

Mössbauer studies of iron hydride at high pressure

NASA Astrophysics Data System (ADS)

Choe, I.; Ingalls, R.; Brown, J. M.; Sato-Sorensen, Y.; Mills, R.

1991-07-01

We have measured in situ Mössbauer spectra of iron hydride made in a diamond anvil cell at high pressure and room temperature. The spectra show a sudden change at 3.5+/-0.5 GPa from a single hyperfine pattern to a superposition of three. The former pattern results from normal α-iron with negligible hydrogen content, and the latter from residual α-iron plus newly formed iron hydride. Between 3.5 and 10.4 GPa, the extra hydride pattern have hyperfine fields for one ranging from 276 to 263 kOe, and the other, from 317 to 309 kOe. Both have isomer shifts of about 0.4 mm/sec, and negligible quadrupole splittings. X-ray studies on quenched samples have shown that iron hydride is of double hexagonal close-packed structure, whose two nonequivalent iron sites may account for the observation of two different patterns. Even allowing for the effect of volume expansion, the observed isomer shifts for the hydride are considerably more positive than those of other metallic phases of iron. At the same time, the hyperfine fields are slightly smaller than that of α-iron. As a possible explanation, one may expect a bonding of hydrogen with iron, which would result in a small reduction of 4s electrons, possibly accompanied by a small increase of 3d electrons compared with the neutral atom in metallic iron. The difference between the hyperfine fields in the two spectra are presumably due to the different symmetry at the two iron sites.

Atomic Spectra and the Vector Model

NASA Astrophysics Data System (ADS)

Candler, A. C.

2015-05-01

12. Displaced terms; 13. Combination of several electrons; 14. Short periods; 15. Long periods; 16. Rare earths; 17. Intensity relsations; 18. Sum rules and (jj) coupling; 19. Series limit; 20. Hyperfine structure; 21. Quadripole radiation; 22. Fluorescent crystals; Appendix 5. Key to references; Appendix 6. Bibliography; Subject index; Author index.

Quantum versus classical hyperfine-induced dynamics in a quantum dota)

NASA Astrophysics Data System (ADS)

Coish, W. A.; Loss, Daniel; Yuzbashyan, E. A.; Altshuler, B. L.

2007-04-01

In this article we analyze spin dynamics for electrons confined to semiconductor quantum dots due to the contact hyperfine interaction. We compare mean-field (classical) evolution of an electron spin in the presence of a nuclear field with the exact quantum evolution for the special case of uniform hyperfine coupling constants. We find that (in this special case) the zero-magnetic-field dynamics due to the mean-field approximation and quantum evolution are similar. However, in a finite magnetic field, the quantum and classical solutions agree only up to a certain time scale t <τc, after which they differ markedly.

The g$$p\\atop{2}$$ Experiment: A Measurement of the Proton's Spin Structure Functions

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

Zielinski, Ryan B.

The E08-027 (gmore » $$p\\atop{2}$$) experiment measured the spin structure functions of the proton at Jefferson Laboratory in Newport News, Va. Longitudinally polarized electrons were scattered from a transversely and longitudinally polarized solid ammonia target in Hall A, with the polarized NH$$_3$$ acting as an effective proton target. Focusing on small scattering angle events at the electron energies available at Jefferson Lab, the experiment covered a kinematic phase space of 0.02 GeV$^2$ $< Q^2 <$ 0.20 GeV$^2$ in the proton's resonance region. The spin structure functions, $$g_{1}^p(x,Q^2)$$ and $$g_{2}^p(x,Q^2)$$ , are extracted from an inclusive polarized cross section measurement of the electron-proton interaction. Integrated moments of $$g_1(x,Q^2)$$ are calculated and compared to theoretical predictions made by Chiral Perturbation Theory. The $$g_1(x,Q^2)$$ results are in agreement with previous measurements, but include a significant increase in statistical precision. The spin structure function contributions to the hyperfine energy levels in the hydrogen atom are also investigated. The $$g_2(x,Q^2)$$ measured contribution to the hyperfine splitting is the first ever experimental determination of this quantity. The results of this thesis suggest a disagreement of over 100% with previously published model results.« less

Hyperfine structure in 229gTh3+ as a probe of the 229gTh→ 229mTh nuclear excitation energy.

PubMed

Beloy, K

2014-02-14

We identify a potential means to extract the 229gTh→ 229mTh nuclear excitation energy from precision microwave spectroscopy of the 5F(5/2,7/2) hyperfine manifolds in the ion 229gTh3+. The hyperfine interaction mixes this ground fine structure doublet with states of the nuclear isomer, introducing small but observable shifts to the hyperfine sublevels. We demonstrate how accurate atomic structure calculations may be combined with the measurement of the hyperfine intervals to quantify the effects of this mixing. Further knowledge of the magnetic dipole decay rate of the isomer, as recently reported, allows an indirect determination of the nuclear excitation energy.

Matrix effects on copper(II)phthalocyanine complexes. A combined continuous wave and pulse EPR and DFT study.

PubMed

Finazzo, Cinzia; Calle, Carlos; Stoll, Stefan; Van Doorslaer, Sabine; Schweiger, Arthur

2006-04-28

The effect of the electron withdrawing or donating character of groups located at the periphery of the phthalocyanine ligand, as well as the influence of polar and nonpolar solvents are of importance for the redox chemistry of metal phthalocyanines. Continuous wave and pulse electron paramagnetic resonance and pulse electron nuclear double resonance spectroscopy at X- and Q-band are applied to investigate the electronic structure of the complexes Cu(II)phthalocyanine (CuPc), copper(II) 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (CuPc(t)), and copper(II) 1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexadecafluoro-29H,31H-phthalocyanine (CuPc(F)) in various matrices. Isotope substitutions are used to determine the g values, the copper hyperfine couplings and the hyperfine interactions with the 14N, 1H and 19F nuclei of the macrocycle and the surrounding matrix molecules. Simulations and interpretations of the spectra are shown and discussed, and a qualitative analysis of the data using previous theoretical models is given. Density functional computations facilitate the interpretation of the EPR parameters. The experimental g, copper and nitrogen hyperfine and nuclear quadrupole values are found to be sensitive to changes of the solvent and the structure of the macrocycle. To elucidate the electronic, structural and bonding properties the changes in the g principal values are related to data from UV/Vis spectroscopy and to density functional theory (DFT) computations. The analysis of the EPR data indicates that the in-plane metal-ligand sigma bonding is more covalent for CuPc(t) in toluene than in sulfuric acid. Furthermore, the out-of-plane pi bonding is found to be less covalent in the case of a polar sulfuric acid environment than with nonpolar toluene or H2Pc environment, whereby the covalency of this bonding is increased upon addition of tert-butyl groups. No contribution from in-plane pi bonding is found.

Confinement and Diffusion Effects in Dynamical Nuclear Polarization in Low Dimensional Nanostructures

NASA Astrophysics Data System (ADS)

Henriksen, Dan; Tifrea, Ionel

2012-02-01

We investigate the dynamic nuclear polarization as it results from the hyperfine coupling between nonequilibrium electronic spins and nuclear spins in semiconductor nanostructures. The natural confinement provided by low dimensional nanostructures is responsible for an efficient nuclear spin - electron spin hyperfine coupling [1] and for a reduced value of the nuclear spin diffusion constant [2]. In the case of optical pumping, the induced nuclear spin polarization is position dependent even in the presence of nuclear spin diffusion. This effect should be measurable via optically induced nuclear magnetic resonance or time-resolved Faraday rotation experiments. We discuss the implications of our calculations for the case of GaAs quantum well structures.[4pt] [1] I. Tifrea and M. E. Flatt'e, Phys. Rev. B 84, 155319 (2011).[0pt] [2] A. Malinowski and R. T. Harley, Solid State Commun. 114, 419 (2000).

Fine- and hyperfine-structure effects in molecular photoionization. II. Resonance-enhanced multiphoton ionization and hyperfine-selective generation of molecular cations

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

Germann, Matthias; Willitsch, Stefan, E-mail: stefan.willitsch@unibas.ch

2016-07-28

Resonance-enhanced multiphoton ionization (REMPI) is a widely used technique for studying molecular photoionization and producing molecular cations for spectroscopy and dynamics studies. Here, we present a model for describing hyperfine-structure effects in the REMPI process and for predicting hyperfine populations in molecular ions produced by this method. This model is a generalization of our model for fine- and hyperfine-structure effects in one-photon ionization of molecules presented in Paper I [M. Germann and S. Willitsch, J. Chem. Phys. 145, 044314 (2016)]. This generalization is achieved by covering two main aspects: (1) treatment of the neutral bound-bound transition including the hyperfine structuremore » that makes up the first step of the REMPI process and (2) modification of our ionization model to account for anisotropic populations resulting from this first excitation step. Our findings may be used for analyzing results from experiments with molecular ions produced by REMPI and may serve as a theoretical background for hyperfine-selective ionization experiments.« less

Low-temperature binding of NO adsorbed on MIL-100(Al)-A case study for the application of high resolution pulsed EPR methods and DFT calculations.

PubMed

Mendt, Matthias; Barth, Benjamin; Hartmann, Martin; Pöppl, Andreas

2017-12-14

The low-temperature binding of nitric oxide (NO) in the metal-organic framework MIL-100(Al) has been investigated by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy. Three NO adsorption species have been identified. Among them, one species has been verified experimentally to bind directly to an 27 Al atom and all its relevant 14 N and 27 Al hyperfine interaction parameters have been determined spectroscopically. Those parameters fit well to the calculated ones of a theoretical cluster model, which was derived by density functional theory (DFT) in the present work and describes the low temperature binding of NO to the regular coordinatively unsaturated Al 3+ site of the MIL-100(Al) structure. As a result, the Lewis acidity of that site has been characterized using the NO molecule as an electron paramagnetic resonance active probe. The DFT derived wave function analysis revealed a bent end-on coordination of the NO molecule adsorbed at that site which is almost purely ionic and has a weak binding energy. The calculated flat potential energy surface of this species indicates the ability of the NO molecule to freely rotate at intermediate temperatures while it is still binding to the Al 3+ site. For the other two NO adsorption species, no structural models could be derived, but one of them is indicated to be adsorbed at the organic part of the metal-organic framework. Hyperfine interactions with protons, weakly coupled to the observed NO adsorption species, have also been measured by pulsed electron paramagnetic resonance and found to be consistent with their attribution to protons of the MIL-100(Al) benzenetricarboxylate ligand molecules.

Correlation effects in fcc-Fe(x)Ni(1-x) alloys investigated by means of the KKR-CPA.

PubMed

Minár, J; Mankovsky, S; Šipr, O; Benea, D; Ebert, H

2014-07-09

The electronic structure and magnetic properties of the disordered alloy system fcc-FexNi1-x (fcc: face centered cubic) have been investigated by means of the KKR-CPA (Korringa-Kohn-Rostoker coherent potential approximation) band structure method. To investigate the impact of correlation effects, the calculations have been performed on the basis of the LSDA (local spin density approximation), the LSDA + U as well as the LSDA + DMFT (dynamical mean field theory). It turned out that the inclusion of correlation effects hardly changed the spin magnetic moments and the related hyperfine fields. The spin-orbit induced orbital magnetic moments and hyperfine fields, on the other hand, show a pronounced and element-specific enhancement. These findings are in full accordance with the results of a recent experimental study.

Nagaoka’s atomic model and hyperfine interactions

PubMed Central

INAMURA, Takashi T.

2016-01-01

The prevailing view of Nagaoka’s “Saturnian” atom is so misleading that today many people have an erroneous picture of Nagaoka’s vision. They believe it to be a system involving a ‘giant core’ with electrons circulating just outside. Actually, though, in view of the Coulomb potential related to the atomic nucleus, Nagaoka’s model is exactly the same as Rutherford’s. This is true of the Bohr atom, too. To give proper credit, Nagaoka should be remembered together with Rutherford and Bohr in the history of the atomic model. It is also pointed out that Nagaoka was a pioneer of understanding hyperfine interactions in order to study nuclear structure. PMID:27063182

Cold Rydberg molecules

NASA Astrophysics Data System (ADS)

Raithel, Georg

2017-04-01

Cold atomic systems have opened new frontiers in atomic and molecular physics, including several types of Rydberg molecules. Three types will be reviewed. Long-range Rydberg-ground molecules, first predicted in and observed in, are formed via low-energy electron scattering of the Rydberg electron from a ground-state atom within the Rydberg atom's volume. The binding mostly arises from S- and P-wave triplet scattering. We use a Fermi model that includes S-wave and P-wave singlet and triplet scattering, the fine structure coupling of the Rydberg atom and the hyperfine structure coupling of the 5S1/2 atom (in rubidium). The hyperfine structure gives rise to mixed singlet-triplet potentials for both low-L and high-L Rydberg molecules. A classification into Hund's cases will be discussed. The talk further includes results on adiabatic potentials and adiabatic states of Rydberg-Rydberg molecules in Rb and Cs. These molecules, which have even larger bonding length than Rydberg-ground molecules, are formed via electrostatic multipole interactions. The leading interaction of neutral Rydberg-Rydberg molecules is dipole-dipole, while for ionic Rydberg molecules it is dipole-monopole. Higher-order terms are discussed. FUNDING: NSF (PHY-1506093), NNSF of China (61475123).

Lamb shifts and hyperfine structure in 6Li+ and 7Li+: Theory and experiment

NASA Astrophysics Data System (ADS)

Riis, E.; Sinclair, A. G.; Poulsen, O.; Drake, G. W. F.; Rowley, W. R. C.; Levick, A. P.

1994-01-01

High-precision laser-resonance measurements accurate to +/-0.5 MHz or better are reported for transitions among the 1s2s 3S1-1s2p 3PJ hyperfine manifolds for each of J=0, 1, and 2 in both 6Li+ and 7Li+. A detailed analysis of hyperfine structure is performed for both the S and P states, using newly calculated values for the magnetic dipole and electric quadrupole coupling constants, and the hyperfine shifts subtracted from the measurements. The resulting transition frequencies are then analyzed on three different levels. First, the isotope shifts in the fine-structure splittings are calculated from the relativistic reduced mass and recoil terms in the Breit interaction, and compared with experiment at the +/-0.5-MHz level of accuracy. This comparison is particularly significant because J-independent theoretical uncertainties reduce through cancellation to the +/-0.01-MHz level. Second, the isotope shifts in the full transition frequencies are used to deduce the difference in rms nuclear radii. The result is Rrms(6Li)-Rrms(7Li)=0.15+/-0.01 fm, in agreement with nuclear scattering data, but with substantially improved accuracy. Third, high-precision calculations of the low-order non-QED contributions to the transition frequencies are subtracted from the measurements to obtain the residual QED shifts. The isotope-averaged and spin-averaged effective shift for 7Li+ is 37 429.40+/-0.39 MHz, with an additional uncertainty of +/-1.5 MHz due to finite nuclear size corrections. The accuracy of 11 parts per million is the best two-electron Lamb shift measurement in the literature, and is comparable to the accuracies achieved in hydrogen. Theoretical contributions to the two-electron Lamb shift are discussed, including terms of order (αZ)4 recently obtained by Chen, Cheng, and Johnson [Phys. Rev. A 47, 3692 (1993)], and the results used to extract a QED shift for the 2 3S1 state. The result of 30 254+/-12 MHz is shown to be in good accord with theory (30 250+/-30 MHz) when two-electron corrections to the Bethe logarithm are taken into account by a 1/Z expansion method.

Niobium hyperfine structure in crystal calcium tungstate

NASA Technical Reports Server (NTRS)

Tseng, D. L.; Kikuchi, C.

1972-01-01

A study of the niobium hyperfine structure in single crystal calcium tungstate was made by the combination of the technique of electron paramagnetic resonance and electron nuclear double resonance (EPR/ENDOR). The microwave frequency was about 9.4 GHz and the radio frequency from 20MHz to 70 MHz. The rare earth ions Nd(3+), U(3+), or Tm(3+) were added as the charge compensator for Nb(5+). To create niobium paramagnetic centers, the sample was irradiated at 77 deg K with a 10 thousand curie Co-60 gamma source for 1 to 2 hours at a dose rate of 200 K rads per hour and then transferred quickly into the cavity. In a general direction of magnetic field, the spectra showed 4 sets of 10 main lines corresponding to 4 nonequivalent sites of niobium with I = 9/2. These 4 sets of lines coalesced into 2 sets of 10 in the ab-plane and into a single set of 10 along the c-axis. This symmetry suggested that the tungsten ions are substituted by the niobium ions in the crystal.

Relativistic coupled-cluster-theory analysis of energies, hyperfine-structure constants, and dipole polarizabilities of Cd+

NASA Astrophysics Data System (ADS)

Li, Cheng-Bin; Yu, Yan-Mei; Sahoo, B. K.

2018-02-01

Roles of electron correlation effects in the determination of attachment energies, magnetic-dipole hyperfine-structure constants, and electric-dipole (E 1 ) matrix elements of the low-lying states in the singly charged cadmium ion (Cd+) have been analyzed. We employ the singles and doubles approximated relativistic coupled-cluster (RCC) method to calculate these properties. Intermediate results from the Dirac-Hartree-Fock approximation,the second-order many-body perturbation theory, and considering only the linear terms of the RCC method are given to demonstrate propagation of electron correlation effects in this ion. Contributions from important RCC terms are also given to highlight the importance of various correlation effects in the evaluation of these properties. At the end, we also determine E 1 polarizabilities (αE 1) of the ground and 5 p 2P1 /2 ;3 /2 states of Cd+ in the ab initio approach. We estimate them again by replacing some of the E 1 matrix elements and energies from the measurements to reduce their uncertainties so that they can be used in the high-precision experiments of this ion.

Determination of the binding energies of the np Rydberg states of H{sub 2}, HD, and D{sub 2} from high-resolution spectroscopic data by multichannel quantum-defect theory

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

Sprecher, Daniel; Merkt, Frédéric, E-mail: frederic.merkt@phys.chem.ethz.ch; Jungen, Christian

2014-03-14

Multichannel quantum-defect theory (MQDT) is used to calculate the electron binding energies of np Rydberg states of H{sub 2}, HD, and D{sub 2} around n = 60 at an accuracy of better than 0.5 MHz. The theory includes the effects of rovibronic channel interactions and the hyperfine structure, and has been extended to the calculation of the asymmetric hyperfine structure of Rydberg states of a heteronuclear diatomic molecule (HD). Starting values for the eigenquantum-defect parameters of MQDT were extracted from ab initio potential-energy functions for the low-lying p Rydberg states of molecular hydrogen and subsequently refined in a global weighted fitmore » to available experimental data on the singlet and triplet Rydberg states of H{sub 2} and D{sub 2}. The electron binding energies of high-np Rydberg states derived in this work represent important quantities for future determinations of the adiabatic ionization energies of H{sub 2}, HD, and D{sub 2} at sub-MHz accuracy.« less

Ground-State Hyperfine Structure of Heavy Hydrogen-Like Ions

NASA Astrophysics Data System (ADS)

Kühl, T.; Borneis, S.; Dax, A.; Engel, T.; Faber, S.; Gerlach, M.; Holbrow, C.; Huber, G.; Marx, D.; Merz, P.; Quint, W.; Schmitt, F.; Seelig, P.; Tomaselli, M.; Winter, H.; Wuertz, M.; Beckert, K.; Franzke, B.; Nolden, F.; Reich, H.; Steck, M.

Contributions of quantum electrodynamics (QED) to the combined electric and magnetic interaction between the electron and the nucleus can be studied by optical spectroscopy in high-Z hydrogen-like heavy ions. The transition studied is the ground-state hyperfine structure transition, well known from the 21 cm line in atomic hydrogen. The hyperfine splitting of the is ground state of hydrogen-like systems constitutes the simplest and most basic magnetic interaction in atomic physics. The Z3-increase leads to a transition energy in the UV-region of the optical spectrum for the case of Bi82+. At the same time, the QED correction rises to nearly 1 fraction of higher order contributions. This situation is particularly useful for a comparison with non-perturbative QED calculations. The combination of exceptionally intense electric and magnetic fields electric and magnetic fields is unique. This transition has become accessible to precision laser spectroscopy at the high-energy heavy-ion storage ring at GSI-Darmstadt in the hydrogen-like 209Bi82+ and 207Pb81+. In the meantime, 165Ho66+ and 185,187Re74+ were also studied with reduced resolution by conventional optical spectroscopy at the SuperEBIT ion trap at Lawrence Livermore National Laboratory.

The nuclear magnetic moment of 208Bi and its relevance for a test of bound-state strong-field QED

NASA Astrophysics Data System (ADS)

Schmidt, S.; Billowes, J.; Bissell, M. L.; Blaum, K.; Garcia Ruiz, R. F.; Heylen, H.; Malbrunot-Ettenauer, S.; Neyens, G.; Nörtershäuser, W.; Plunien, G.; Sailer, S.; Shabaev, V. M.; Skripnikov, L. V.; Tupitsyn, I. I.; Volotka, A. V.; Yang, X. F.

2018-04-01

The hyperfine structure splitting in the 6p3 3/2 4S → 6p2 7 s 1/2 4P transition at 307 nm in atomic 208Bi was measured with collinear laser spectroscopy at ISOLDE, CERN. The hyperfine A and B factors of both states were determined with an order of magnitude improved accuracy. Based on these measurements, theoretical input for the hyperfine structure anomaly, and results from hyperfine measurements on hydrogen-like and lithium-like 209Bi80+,82+, the nuclear magnetic moment of 208Bi has been determined to μ (208Bi) = + 4.570 (10)μN. Using this value, the transition energy of the ground-state hyperfine splitting in hydrogen-like and lithium-like 208Bi80+,82+ and their specific difference of -67.491(5)(148) meV are predicted. This provides a means for an experimental confirmation of the cancellation of nuclear structure effects in the specific difference in order to exclude such contributions as the cause of the hyperfine puzzle, the recently reported 7-σ discrepancy between experiment and bound-state strong-field QED calculations of the specific difference in the hyperfine structure splitting of 209Bi80+,82+.

Hyperfine structure of the MnH X 7Sigma + state: A large gas-to-matrix shift in the Fermi contact interaction

NASA Astrophysics Data System (ADS)

Varberg, Thomas D.; Field, Robert W.; Merer, Anthony J.

1990-06-01

Sub-Doppler spectra of the A 7Π-X 7Σ+ (0,0) band of gas phase MnH near 5680 Å were recorded by intermodulated fluorescence spectroscopy. The spectra reveal hyperfine splittings arising from both the 55Mn and 1H nuclear spins. Internal hyperfine perturbations have been observed between the different spin components of the ground state at low N`. From a preliminary analysis of several rotational lines originating from the isolated and unperturbed F1(J`=3) spin component of the X 7Σ+(N`=0) level, the 55Mn Fermi contact interaction in the ground state has been measured as bF=Aiso =276(1) MHz. This value is 11% smaller than the value obtained by Weltner et al. from an electron-nuclear double resonance (ENDOR) study of MnH in an argon matrix at 4 K. This unprecedented gas-to-matrix shift in the Fermi contact parameter is discussed.

Synthesis, X-ray structure, magnetic resonance, and DFT analysis of a soluble copper(II) phthalocyanine lacking C-H bonds.

PubMed

Moons, Hans; Łapok, Łukasz; Loas, Andrei; Van Doorslaer, Sabine; Gorun, Sergiu M

2010-10-04

The synthesis, crystal structure, and electronic properties of perfluoro-isopropyl-substituted perfluorophthalocyanine bearing a copper atom in the central cavity (F(64)PcCu) are reported. While most halogenated phthalocyanines do not exhibit long-term order sufficient to form large single crystals, this is not the case for F(64)PcCu. Its crystal structure was determined by X-ray analysis and linked to the electronic properties determined by electron paramagnetic resonance (EPR). The findings are corroborated by density functional theory (DFT) computations, which agree well with the experiment. X-band continuous-wave EPR spectra of undiluted F(64)PcCu powder, indicate the existence of isolated metal centers. The electron-withdrawing effect of the perfluoroalkyl (R(f)) groups significantly enhances the complexes solubility in organic solvents like alcohols, including via their axial coordination. This coordination is confirmed by X-band (1)H HYSCORE experiments and is also seen in the solid state via the X-ray structure. Detailed X-band CW-EPR, X-band Davies and Mims ENDOR, and W-band electron spin-echo-detected EPR studies of F(64)PcCu in ethanol allow the determination of the principal g values and the hyperfine couplings of the metal, nitrogen, and fluorine nuclei. Comparison of the g and metal hyperfine values of F(64)PcCu and other PcCu complexes in different matrices reveals a dominant effect of the matrix on these EPR parameters, while variations in the ring substituents have only a secondary effect. The relatively strong axial coordination occurs despite the diminished covalency of the C-N bonds and potentially weakening Jahn-Teller effects. Surprisingly, natural abundance (13)C HYSCORE signals could be observed for a frozen ethanol solution of F(64)PcCu. The (13)C nuclei contributing to the HYSCORE spectra could be identified as the pyrrole carbons by means of DFT. Finally, (19)F ENDOR and easily observable paramagnetic NMR were found to relate well to the DFT computations, revealing negligible isotropic hyperfine (Fermi contact) contributions. The single-site isolation in solution and solid state and the relatively strong coordination of axial ligands, both attributed to the introduction of R(f) groups, are features important for materials and catalyst design.

EPR study of a gamma-irradiated (2-hydroxyethyl)triphenylphosphonium chloride single crystal

NASA Astrophysics Data System (ADS)

Karakaş, E.; Türkkan, E.; Dereli, Ö.; Sayιn, Ü.; Tapramaz, R.

2011-12-01

In this study, gamma-irradiated single crystals of (2-hydroxyethyl)triphenylphosphonium chloride [CH2CH2OH P(C6H5)3Cl] were investigated with electron paramagnetic resonance (EPR) spectroscopy at room temperature for different orientations in the magnetic field. The single crystals were irradiated with a 60Co-γ-ray source at 0.818 kGy/h for about 36 h. Taking the chemical structure and the experimental spectra of the irradiated single crystal of the title compound into consideration, a paramagnetic species was produced with the unpaired electron delocalized around 31P and several 1H nuclei. The anisotropic hyperfine values due to the 31P nucleus, slightly anisotropic hyperfine values due to the 1H nuclei and the g-tensor of the radical were measured from the spectra. Depending on the molecular structure and measured parameters, three possible radicals were modeled using the B3LYP/6-31+G(d) level of density-functional theory, and EPR parameters were calculated for modeled radicals using the B3LYP/TZVP method/basis set combination. The calculated hyperfine coupling constants were found to be in good agreement with the observed EPR parameters. The experimental and theoretically simulated spectra for each of the three crystallographic axes were well matched with one of the modeled radicals (discussed in the text). We thus identified the radical C˙H2CH2 P(C 6H5)3 Cl as a paramagnetic species produced in a single crystal of the title compound in two magnetically distinct sites. The experimental g-factor and hyperfine coupling constants of the radical were found to be anisotropic, with the isotropic values g iso = 2.0032, ? G, ? G, ? G and ? G for site 1 and g iso=2.0031, ? G, ? G ? G and ? G for site 2.

Electronic and Magnetic Structures, Magnetic Hyperfine Fields and Electric Field Gradients in UX3 (X = In, Tl, Pb) Intermetallic Compounds

NASA Astrophysics Data System (ADS)

Khan, Sajid; Yazdani-Kachoei, Majid; Jalali-Asadabadi, Saeid; Farooq, Muhammad Bilal; Ahmad, Iftikhar

2018-02-01

Cubic uranium compounds such as UX3 (X is a non-transition element of groups IIIA or IVA) exhibit highly diverse magnetic properties, including Pauli paramagnetism, spin fluctuation and anti-ferromagnetism. In the present paper, we explore the structural, electronic and magnetic properties as well as the hyperfine fields (HFFs) and electric field gradients (EFGs) with quadrupole coupling constant of UX3 (X = In, Tl, Pb) compounds using local density approximation, Perdew-Burke-Ernzerhof parametrization of generalized gradient approximation (PBE-GGA) including the Hubbard U parameter (GGA + U), a revised version of PBE-GGA that improves equilibrium properties of densely packed solids and their surfaces (PBEsol-GGA), and a hybrid functional (HF-PBEsol). The spin orbit-coupling calculations have been added to investigate the relativistic effect of electrons in these materials. The comparison between the experimental parameters and our calculated structural parameters we confirm the consistency and effectiveness of our theoretical tools. The computed magnetic moments show that magnetic moment increases from indium to lead in the UX3 family, and all these compounds are antiferromagnetic in nature. The EFGs and HFFs, as well as the quadrupole coupling constant of UX3 (X = In, Tl, Pb), are discussed in detail. These properties primarily originate from f and p states of uranium and post-transition sites.

Charge radii and electromagnetic moments of At-211195

NASA Astrophysics Data System (ADS)

Cubiss, J. G.; Barzakh, A. E.; Seliverstov, M. D.; Andreyev, A. N.; Andel, B.; Antalic, S.; Ascher, P.; Atanasov, D.; Beck, D.; Bieroń, J.; Blaum, K.; Borgmann, Ch.; Breitenfeldt, M.; Capponi, L.; Cocolios, T. E.; Day Goodacre, T.; Derkx, X.; De Witte, H.; Elseviers, J.; Fedorov, D. V.; Fedosseev, V. N.; Fritzsche, S.; Gaffney, L. P.; George, S.; Ghys, L.; Heßberger, F. P.; Huyse, M.; Imai, N.; Kalaninová, Z.; Kisler, D.; Köster, U.; Kowalska, M.; Kreim, S.; Lane, J. F. W.; Liberati, V.; Lunney, D.; Lynch, K. M.; Manea, V.; Marsh, B. A.; Mitsuoka, S.; Molkanov, P. L.; Nagame, Y.; Neidherr, D.; Nishio, K.; Ota, S.; Pauwels, D.; Popescu, L.; Radulov, D.; Rapisarda, E.; Revill, J. P.; Rosenbusch, M.; Rossel, R. E.; Rothe, S.; Sandhu, K.; Schweikhard, L.; Sels, S.; Truesdale, V. L.; Van Beveren, C.; Van den Bergh, P.; Wakabayashi, Y.; Van Duppen, P.; Wendt, K. D. A.; Wienholtz, F.; Whitmore, B. W.; Wilson, G. L.; Wolf, R. N.; Zuber, K.

2018-05-01

Hyperfine-structure parameters and isotope shifts of At-211195 have been measured for the first time at CERN-ISOLDE, using the in-source resonance-ionization spectroscopy method. The hyperfine structures of isotopes were recorded using a triad of experimental techniques for monitoring the photo-ion current. The Multi-Reflection Time-of-Flight Mass Spectrometer, in connection with a high-resolution electron multiplier, was used as an ion-counting setup for isotopes that either were affected by strong isobaric contamination or possessed a long half-life; the ISOLDE Faraday cups were used for cases with high-intensity beams; and the Windmill decay station was used for short-lived, predominantly α -decaying nuclei. The electromagnetic moments and changes in the mean-square charge radii of the astatine nuclei have been extracted from the measured hyperfine-structure constants and isotope shifts. This was only made possible by dedicated state-of-the-art large-scale atomic computations of the electronic factors and the specific mass shift of atomic transitions in astatine that are needed for these extractions. By comparison with systematics, it was possible to assess the reliability of the results of these calculations and their ascribed uncertainties. A strong deviation in the ground-state mean-square charge radii of the lightest astatine isotopes, from the trend of the (spherical) lead isotopes, is interpreted as the result of an onset of deformation. This behavior bears a resemblance to the deviation observed in the isotonic polonium isotopes. Cases for shape coexistence have been identified in At,199197, for which a significant difference in the charge radii for ground (9 /2- ) and isomeric (1 /2+ ) states has been observed.

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 radiation. Here, the laser pulse merely defines the beginning of the microwave-induced coherent time evolution. This second mechanism appears the most consistent with current experimental observations.

Reanalysis and extension of the MnH A7Π- X7Σ + (0, 0) band: Fine structure and hyperfine-induced rotational branches

NASA Astrophysics Data System (ADS)

Varberg, Thomas D.; Gray, Jeffrey A.; Field, Robert W.; Merer, Anthony J.

1992-12-01

The A7Π- X7Σ + (0, 0) band of MnH at 568 nm has been recorded by laser fluorescence excitation spectroscopy. The original rotational analysis of Nevin [ Proc. R. Irish Acad.48A, 1-45 (1942); 50A, 123-137 (1945)] has been extended with some corrections at low J. Systematic internal hyperfine perturbations in the X7Σ + state, caused by the Δ N = 0, Δ J = ±1 matrix elements of the 55Mn hyperfine term in the Hamiltonian, have been observed in all seven electron spin components over the entire range of N″ studied. These perturbations destroy the "goodness" of J″ as a quantum number, giving rise to hyperfine-induced Δ J = ±2 rotational branches and to observable energy shifts of the most severely affected levels. The A7Π state, with A = 40.5 cm -1 and B = 6.35 cm -1, evolves rapidly from Hund's case ( a) to case ( b) coupling, which produces anomalous branch patterns at low J. A total of 156 rotational branches have been identified and fitted by least squares to an effective Hamiltonian, providing precise values for the rotational and fine structure constants. Values of the principal constants determined in the fit are (1σ errors in units of the last digit are listed in parentheses): The fine structures of the A7Π and X7Σ + states confirm the assignment of the A ← X transition as Mn 4 pπ ← 4 sσ in the presence of a spectator, nonbonding Mn 3 d5 ( 6S) open core.

Hyperfine Structure and Exchange Narrowing of Paramagnetic Resonance

DOE R&D Accomplishments Database

Townes, C. H.; Turkevich, J.

1950-01-01

Discussion of electronic paramagnetic resonance for the free radical ?, ?-diphenyl ?-picryl hydrazyl as observed by its effect on the transmission of microwave through a TE{sub 01} cavity with a small amount of the free radical placed approximately on the axis of the cavity; the half-width of this resonance at half maximum absorption was 1.45 oersteds.

High precision hyperfine measurements in Bismuth challenge bound-state strong-field QED

PubMed Central

Ullmann, Johannes; Andelkovic, Zoran; Brandau, Carsten; Dax, Andreas; Geithner, Wolfgang; Geppert, Christopher; Gorges, Christian; Hammen, Michael; Hannen, Volker; Kaufmann, Simon; König, Kristian; Litvinov, Yuri A.; Lochmann, Matthias; Maaß, Bernhard; Meisner, Johann; Murböck, Tobias; Sánchez, Rodolfo; Schmidt, Matthias; Schmidt, Stefan; Steck, Markus; Stöhlker, Thomas; Thompson, Richard C.; Trageser, Christian; Vollbrecht, Jonas; Weinheimer, Christian; Nörtershäuser, Wilfried

2017-01-01

Electrons bound in highly charged heavy ions such as hydrogen-like bismuth 209Bi82+ experience electromagnetic fields that are a million times stronger than in light atoms. Measuring the wavelength of light emitted and absorbed by these ions is therefore a sensitive testing ground for quantum electrodynamical (QED) effects and especially the electron–nucleus interaction under such extreme conditions. However, insufficient knowledge of the nuclear structure has prevented a rigorous test of strong-field QED. Here we present a measurement of the so-called specific difference between the hyperfine splittings in hydrogen-like and lithium-like bismuth 209Bi82+,80+ with a precision that is improved by more than an order of magnitude. Even though this quantity is believed to be largely insensitive to nuclear structure and therefore the most decisive test of QED in the strong magnetic field regime, we find a 7-σ discrepancy compared with the theoretical prediction. PMID:28508892

Electron spin resonance identification di-carbon-related centers in irradiated silicon

NASA Astrophysics Data System (ADS)

Hayashi, S.; Saito, H.; Itoh, K. M.; Vlasenko, M. P.; Vlasenko, L. S.

2018-04-01

A previously unreported electron spin resonance (ESR) spectrum was found in γ-ray irradiated silicon by the detection of the change in microwave photoconductivity arising from spin-dependent recombination (SDR). In the specially prepared silicon crystals doped by 13C isotope, a well resolved hyperfine structure of SDR-ESR lines due to the interaction between electrons and two equivalent carbon atoms having nuclear spin I = 1/2 was observed. The Si-KU4 spectrum is described by spin Hamiltonian for spin S = 1 and of g and D tensors of orthorhombic symmetry with principal values g1 = 2.008, g2 = 2.002, and g3 =2.007; and D1 = ± 103 MHz, D2 = ∓170 MHz, and D3 = ± 67 MHz where axes 1, 2, and 3 are parallel to the [1 1 ¯ 0 ], [110], and [001] crystal axes, respectively. The hyperfine splitting arising from 13C nuclei is about 0.35 mT. A possible microstructure of the detect leading to the Si-KU4 spectrum is discussed.

Ground-state hyperfine splitting for Rb, Cs, Fr, Ba+, and Ra+

NASA Astrophysics Data System (ADS)

Ginges, J. S. M.; Volotka, A. V.; Fritzsche, S.

2017-12-01

We have systematically investigated the ground-state hyperfine structure for alkali-metal atoms 87Rb,133Cs, and 211Fr and alkali-metal-like ions +135Ba and +225Ra, which are of particular interest for parity violation studies. The quantum electrodynamic one-loop radiative corrections have been rigorously evaluated within an extended Furry picture employing core-Hartree and Kohn-Sham atomic potentials. Moreover, the effect of the nuclear magnetization distribution on the hyperfine structure intervals has been studied in detail and its uncertainty has been estimated. Finally, the theoretical description of the hyperfine structure has been completed with full many-body calculations performed in the all-orders correlation potential method.

Hyperfine structure of excited states and quadrupole moment of Ne-21 using laser-induced line-narrowing techniques.

NASA Technical Reports Server (NTRS)

Ducas, T. W.; Feld, M. S.; Ryan, L. W., Jr.; Skribanowitz, N.; Javan, A.

1972-01-01

Observation results are presented on the optical hyperfine structure in Ne-21 obtained with the aid of laser-induced line-narrowing techniques. The output from a long stabilized single-mode 1.15-micron He-Ne laser focused into an external sample cell containing Ne-21 was used in implementing these techniques. Their applicability is demonstrated for optical hyperfine structure observation in systems whose features are ordinarily masked by Doppler broadening.

Electronic structure and magnetic properties of disordered Co{sub 2}FeAl Heusler alloy

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

Jain, Vishal, E-mail: vjain045@gmail.com; Jain, Vivek, E-mail: vjain045@gmail.com; Sudheesh, V. D., E-mail: vjain045@gmail.com

The effects of disorder on the magnetic properties of Co{sub 2}FeAl alloy are reported. X-ray diffraction exhibit A2-type disordered structure. Room temperature Mössbauer studies show the presence of two sextets with hyperfine field values of 31T and 30T along with a nonmagnetic singlet. The electronic structure of ordered and disordered Co{sub 2}FeAl alloys, investigated by means of the KKR Green's-function method shows that the magnetic moment of the ordered structure is 5.08μ{sub B} and is 5.10μ{sub B} when disordered. However, a much higher magnetic moment of 5.74μ{sub B} is observed experimentally.

Calculation of the spin-polarized electronic structure of an interstitial iron impurity in silicon

NASA Astrophysics Data System (ADS)

Katayama-Yoshida, H.; Zunger, Alex

1985-06-01

We apply our self-consistent, all-electron, spin-polarized Green's-function method within an impurity-centered, dynamic basis set to study the interstitial iron impurity in silicon. We use two different formulations of the interelectron interactions: the local-spin-density (LSD) formalism and the self-interaction-corrected (SIC) local-spin-density (SIC-LSD) formalism. We find that the SIC-LSD approach is needed to obtain the correct high-spin ground state of Si:Fe+. We propose a quantitative explanation to the observed donor ionization energy and the high-spin ground states for Si:Fe+ within the SIC-LSD approach. For both Si:Fe0 and Si:Fe+, this approach leads to a hyperfine field, contact spin density, and ionization energy in better agreement with experiments than the simple LSD approach. The apparent dichotomy between the covalently delocalized nature of Si:Fe as suggested on the one hand by its reduced hyperfine field (relative to the free atom) and extended spin density and by the occurrence of two closely spaced, stable charge states (within 0.4 eV) and on the other hand by the atomically localized picture (suggested, for example, by the stability of a high-spin, ground-state configuration) is resolved. We find a large reduction in the hyperfine field and contact spin density due to the covalent hybridization between the impurity 3d orbitals and the tails of the delocalized sp3 hybrid orbitals of the surrounding silicon atoms. Using the calculated results, we discuss (i) the underlying mechanism for the stability and plurality of charged states, (ii) the covalent reduction in the hyperfine field, (iii) the remarkable constancy of the impurity Mössbauer isomer shift for different charged states, (iv) comparison with the multiple charged states in ionic crystals, and (v) some related speculation about the mechanism of (Fe2+/Fe3+) oxidation-reduction ionizations in heme proteins and electron-transporting biological systems.

Cold Rydberg molecules

NASA Astrophysics Data System (ADS)

Raithel, Georg; Zhao, Jianming

2017-04-01

Cold atomic systems have opened new frontiers at the interface of atomic and molecular physics. These include research on novel types of Rydberg molecules. Three types of molecules will be reviewed. Long-range, homonuclear Rydberg molecules, first predicted in [1] and observed in [2], are formed via low-energy electron scattering of the Rydberg electron from a ground-state atom within the Rydberg atom's volume. The binding mostly arises from S- and P-wave triplet scattering. We use a Fermi model that includes S-wave and P-wave singlet and triplet scattering, the fine structure coupling of the Rydberg atom and the hyperfine structure coupling of the 5S1/2 atom (in rubidium [3]). The hyperfine structure gives rise to mixed singlet-triplet potentials for both low-L and high-L Rydberg molecules [3]. A classification into Hund's cases [3, 4, 5] will be discussed. The talk further includes results on adiabatic potentials and adiabatic states of Rydberg-Rydberg molecules in Rb and Cs. These molecules, which have even larger bonding length than Rydberg-ground molecules, are formed via electrostatic multipole interactions. The leading interaction term of neutral Rydberg-Rydberg molecules is between two dipoles, while for ionic Rydberg molecules it is between a dipole and a monopole. NSF (PHY-1506093), NNSF of China (61475123).

Structural investigation and electron paramagnetic resonance of vanadyl doped alkali niobium borate glasses.

PubMed

Agarwal, A; Sheoran, A; Sanghi, S; Bhatnagar, V; Gupta, S K; Arora, M

2010-03-01

Glasses with compositions xNb(2)O(5).(30-x)M(2)O.69B(2)O(3) (where M=Li, Na, K; x=0, 4, 8 mol%) doped with 1 mol% V(2)O(5) have been prepared using normal melt quench technique. The IR transmission spectra of the glasses have been studied over the range 400-4000 cm(-1). The changes caused by the addition of Nb(2)O(5) on the structure of these glasses have been reported. The electron paramagnetic resonance spectra of VO(2+) ions in these glasses have been recorded in X-band (9.14 GHz) at room temperature (300 K). The spin Hamiltonian parameters, dipolar hyperfine coupling parameter and Fermi contact interaction parameter have been calculated. It is observed that the resultant resonance spectra contain hyperfine structures (hfs) due to V(4+) ions which exist as VO(2+) ions in octahedral coordination with a tetragonal compression in the present glasses. The tetragonality of V(4+)O(6) complex decreases with increasing concentration of Nb(2)O(5). The 3d(xy) orbit contracts with increase in Nb(2)O(5):M(2)O ratio. Values of the theoretical optical basicity, Lambda(th), have also been reported. Copyright 2009 Elsevier B.V. All rights reserved.

Calculating hyperfine couplings in large ionic crystals containing hundreds of QM atoms: subsystem DFT is the key.

PubMed

Kevorkyants, Ruslan; Wang, Xiqiao; Close, David M; Pavanello, Michele

2013-11-14

We present an application of the linear scaling frozen density embedding (FDE) formulation of subsystem DFT to the calculation of isotropic hyperfine coupling constants (hfcc's) of atoms belonging to a guanine radical cation embedded in a guanine hydrochloride monohydrate crystal. The model systems range from an isolated guanine to a 15,000 atom QM/MM cluster where the QM region is comprised of 36 protonated guanine cations, 36 chlorine anions, and 42 water molecules. Our calculations show that the embedding effects of the surrounding crystal cannot be reproduced by small model systems nor by a pure QM/MM procedure. Instead, a large QM region is needed to fully capture the complicated nature of the embedding effects in this system. The unprecedented system size for a relativistic all-electron isotropic hfcc calculation can be approached in this work because the local nature of the electronic structure of the organic crystals considered is fully captured by the FDE approach.

Effect of WO3 on EPR, structure and electrical conductivity of vanadyl doped WO3·M2O·B2O3 (M=Li, Na) glasses

NASA Astrophysics Data System (ADS)

Sheoran, A.; Agarwal, A.; Sanghi, S.; Seth, V. P.; Gupta, S. K.; Arora, M.

2011-12-01

Glasses with composition xWO3·(30-x)M2O·70B2O3 (M=Li, Na; 0≤x≤15) doped with 2 mol% V2O5 have been prepared using the melt-quench technique. The electron paramagnetic resonance spectra have been recorded in X-band (ν≈9.14 GHz) at room temperature (RT). The spin Hamiltonian parameters, dipolar hyperfine coupling parameter and Fermi contact interaction parameter have been calculated. It is observed that the resultant resonance spectra contain hyperfine structures (hfs) only due to V4+ ions, which exist as VO2+ ions in octahedral coordination with a tetragonal compression in the present glass system. The tetragonality increases with WO3:M2O ratio and also there is an expansion of 3dxy orbit of unpaired electron in the vanadium ion. The study of IR transmission spectra over a range 400-4000 cm-1 depicts the presence of WO6 group. The DC conductivity (σ) has been measured in the temperature range 423-623 K and is found to be predominantly ionic.

Assignment of selected hyperfine proton NMR resonances in the met forms of Glycera dibranchiata monomer hemoglobins and comparisons with sperm whale metmyoglobin

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

Constantinidis, I.; Satterlee, J.D.; Pandey, R.K.

1988-04-19

This work indicates a high degree of purity for our preparations of all three of the primary Glycera dibranchiata monomer hemoglobins and details assignments of the heme methyl and vinyl protons in the hyperfine shift region of the ferric (aquo.) protein forms. The assignments were carried out by reconstituting the apoproteins of each component with selectively deuteriated hemes. The results indicate that even though the individual component preparations consist of essentially a single protein, the proton NMR spectra indicate spectroscopic heterogeneity. Evidence is presented for identification and classification of major and minor protein forms that are present in solutions ofmore » each component. Finally, in contrast to previous results, a detailed analysis of the proton hyperfine shift patterns of the major and minor forms of each component, in comparison to the major and minor forms of metmyoglobin, leads to the conclusions that the corresponding forms of the proteins from each species have strikingly similar heme-globin contacts and display nearly identical heme electronic structures and coordination numbers.« less

29Si-NMR study of magnetic anisotropy and hyperfine interactions in the uranium-bsed ferromagnet UNiSi2

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

Sakai, Hironori; Baek, Seung H; Bauer, Eric D

2009-01-01

UNiSi{sub 2} orders ferromagnetically below T{sub Curie} = 95 K. This material crystallizes in the orthorhombic CeNiSi{sub 2}-type structure. The uranium atoms form double-layers, which are stacked along the crystallographic b axis (the longest axis). From magnetization measurement the easy (hard) magnetization axis is found to be the c axis (b axis). {sup 29}Si-NMR measurements have been performed in the paramagnetic state. In UNiSi{sub 2}, two crystallographic Si sites exist with orthorhombic local symmetry. The Knight shifts on each Si site have been estimated from the spectra of random and oriented powders. The transferred hyperfine couplings have been also derived.more » It is found that the transferred hyperfine coupling constants on each Si site are nearly isotropic, and that their Knight shift anisotropy comes from that of the bulk susceptibility. The nuclear-spin lattice relaxation rate 1/T{sub 1} shows temperature-independent behavior, which indicates the existence of localized 5f electron.« less

Stochastic hyperfine interactions modeling library

NASA Astrophysics Data System (ADS)

Zacate, Matthew O.; Evenson, William E.

2011-04-01

The stochastic hyperfine interactions modeling library (SHIML) provides a set of routines to assist in the development and application of stochastic models of hyperfine interactions. The library provides routines written in the C programming language that (1) read a text description of a model for fluctuating hyperfine fields, (2) set up the Blume matrix, upon which the evolution operator of the system depends, and (3) find the eigenvalues and eigenvectors of the Blume matrix so that theoretical spectra of experimental techniques that measure hyperfine interactions can be calculated. The optimized vector and matrix operations of the BLAS and LAPACK libraries are utilized; however, there was a need to develop supplementary code to find an orthonormal set of (left and right) eigenvectors of complex, non-Hermitian matrices. In addition, example code is provided to illustrate the use of SHIML to generate perturbed angular correlation spectra for the special case of polycrystalline samples when anisotropy terms of higher order than A can be neglected. Program summaryProgram title: SHIML Catalogue identifier: AEIF_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEIF_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU GPL 3 No. of lines in distributed program, including test data, etc.: 8224 No. of bytes in distributed program, including test data, etc.: 312 348 Distribution format: tar.gz Programming language: C Computer: Any Operating system: LINUX, OS X RAM: Varies Classification: 7.4 External routines: TAPP [1], BLAS [2], a C-interface to BLAS [3], and LAPACK [4] Nature of problem: In condensed matter systems, hyperfine methods such as nuclear magnetic resonance (NMR), Mössbauer effect (ME), muon spin rotation (μSR), and perturbed angular correlation spectroscopy (PAC) measure electronic and magnetic structure within Angstroms of nuclear probes through the hyperfine interaction. When interactions fluctuate at rates comparable to the time scale of a hyperfine method, there is a loss in signal coherence, and spectra are damped. The degree of damping can be used to determine fluctuation rates, provided that theoretical expressions for spectra can be derived for relevant physical models of the fluctuations. SHIML provides routines to help researchers quickly develop code to incorporate stochastic models of fluctuating hyperfine interactions in calculations of hyperfine spectra. Solution method: Calculations are based on the method for modeling stochastic hyperfine interactions for PAC by Winkler and Gerdau [5]. The method is extended to include other hyperfine methods following the work of Dattagupta [6]. The code provides routines for reading model information from text files, allowing researchers to develop new models quickly without the need to modify computer code for each new model to be considered. Restrictions: In the present version of the code, only methods that measure the hyperfine interaction on one probe spin state, such as PAC, μSR, and NMR, are supported. Running time: Varies

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.

Using Hyperfine Electron Paramagnetic Resonance Spectroscopy to Define the Proton-Coupled Electron Transfer Reaction at Fe-S Cluster N2 in Respiratory Complex I.

PubMed

Le Breton, Nolwenn; Wright, John J; Jones, Andrew J Y; Salvadori, Enrico; Bridges, Hannah R; Hirst, Judy; Roessler, Maxie M

2017-11-15

Energy-transducing respiratory complex I (NADH:ubiquinone oxidoreductase) is one of the largest and most complicated enzymes in mammalian cells. Here, we used hyperfine electron paramagnetic resonance (EPR) spectroscopic methods, combined with site-directed mutagenesis, to determine the mechanism of a single proton-coupled electron transfer reaction at one of eight iron-sulfur clusters in complex I, [4Fe-4S] cluster N2. N2 is the terminal cluster of the enzyme's intramolecular electron-transfer chain and the electron donor to ubiquinone. Because of its position and pH-dependent reduction potential, N2 has long been considered a candidate for the elusive "energy-coupling" site in complex I at which energy generated by the redox reaction is used to initiate proton translocation. Here, we used hyperfine sublevel correlation (HYSCORE) spectroscopy, including relaxation-filtered hyperfine and single-matched resonance transfer (SMART) HYSCORE, to detect two weakly coupled exchangeable protons near N2. We assign the larger coupling with A( 1 H) = [-3.0, -3.0, 8.7] MHz to the exchangeable proton of a conserved histidine and conclude that the histidine is hydrogen-bonded to N2, tuning its reduction potential. The histidine protonation state responds to the cluster oxidation state, but the two are not coupled sufficiently strongly to catalyze a stoichiometric and efficient energy transduction reaction. We thus exclude cluster N2, despite its proton-coupled electron transfer chemistry, as the energy-coupling site in complex I. Our work demonstrates the capability of pulse EPR methods for providing detailed information on the properties of individual protons in even the most challenging of energy-converting enzymes.

Hyperfine interactions in titanates: Study of orbital ordering and local magnetic properties

NASA Astrophysics Data System (ADS)

Agzamova, P. A.; Leskova, Yu. V.; Nikiforov, A. E.

2013-05-01

Hyperfine magnetic fields induced on the nuclei of nonmagnetic ions 139La and 89Y in LaTiO3 and YTiO3, respectively, have been microscopically calculated. The dependence of the hyperfine fields on the orbital and magnetic structures of the compounds under study has been analyzed. The comparative analysis of the calculated and known experimental data confirms the existence of the static orbital structure in lanthanum and yttrium titanates.

Constraints on Exotic Spin-Dependent Interactions Between Matter and Antimatter from Antiprotonic Helium Spectroscopy

NASA Astrophysics Data System (ADS)

Ficek, Filip; Fadeev, Pavel; Flambaum, Victor V.; Jackson Kimball, Derek F.; Kozlov, Mikhail G.; Stadnik, Yevgeny V.; Budker, Dmitry

2018-05-01

Heretofore undiscovered spin-0 or spin-1 bosons can mediate exotic spin-dependent interactions between standard model particles. Here, we carry out the first search for semileptonic spin-dependent interactions between matter and antimatter. We compare theoretical calculations and spectroscopic measurements of the hyperfine structure of antiprotonic helium to constrain exotic spin- and velocity-dependent interactions between electrons and antiprotons.

Constraints on Exotic Spin-Dependent Interactions Between Matter and Antimatter from Antiprotonic Helium Spectroscopy.

PubMed

Ficek, Filip; Fadeev, Pavel; Flambaum, Victor V; Jackson Kimball, Derek F; Kozlov, Mikhail G; Stadnik, Yevgeny V; Budker, Dmitry

2018-05-04

Heretofore undiscovered spin-0 or spin-1 bosons can mediate exotic spin-dependent interactions between standard model particles. Here, we carry out the first search for semileptonic spin-dependent interactions between matter and antimatter. We compare theoretical calculations and spectroscopic measurements of the hyperfine structure of antiprotonic helium to constrain exotic spin- and velocity-dependent interactions between electrons and antiprotons.

Quantum Theory of Hyperfine Structure Transitions in Diatomic Molecules.

ERIC Educational Resources Information Center

Klempt, E.; And Others

1979-01-01

Described is an advanced undergraduate laboratory experiment in which radio-frequency transitions between molecular hyperfine structure states may be observed. Aspects of the quantum theory applied to the analysis of this physical system, are discussed. (Authors/BT)

Density functional calculations of (55)Mn, (14)N and (13)C electron paramagnetic resonance parameters support an energetically feasible model system for the S(2) state of the oxygen-evolving complex of photosystem II.

PubMed

Schinzel, Sandra; Schraut, Johannes; Arbuznikov, Alexei V; Siegbahn, Per E M; Kaupp, Martin

2010-09-10

Metal and ligand hyperfine couplings of a previously suggested, energetically feasible Mn(4)Ca model cluster (SG2009(-1)) for the S(2) state of the oxygen-evolving complex (OEC) of photosystem II (PSII) have been studied by broken-symmetry density functional methods and compared with other suggested structural and spectroscopic models. This was carried out explicitly for different spin-coupling patterns of the S=1/2 ground state of the Mn(III)(Mn(IV))(3) cluster. By applying spin-projection techniques and a scaling of the manganese hyperfine couplings, computation of the hyperfine and nuclear quadrupole coupling parameters allows a direct evaluation of the proposed models in comparison with data obtained from the simulation of EPR, ENDOR, and ESEEM spectra. The computation of (55)Mn hyperfine couplings (HFCs) for SG2009(-1) gives excellent agreement with experiment. However, at the current level of spin projection, the (55)Mn HFCs do not appear sufficiently accurate to distinguish between different structural models. Yet, of all the models studied, SG2009(-1) is the only one with the Mn(III) site at the Mn(C) center, which is coordinated by histidine (D1-His332). The computed histidine (14)N HFC anisotropy for SG2009(-1) gives much better agreement with ESEEM data than the other models, in which Mn(C) is an Mn(IV) site, thus supporting the validity of the model. The (13)C HFCs of various carboxylates have been compared with (13)C ENDOR data for PSII preparations with (13)C-labelled alanine.

Theory of long-range interactions for Rydberg states attached to hyperfine-split cores

NASA Astrophysics Data System (ADS)

Robicheaux, F.; Booth, D. W.; Saffman, M.

2018-02-01

The theory is developed for one- and two-atom interactions when the atom has a Rydberg electron attached to a hyperfine-split core state. This situation is relevant for some of the rare-earth and alkaline-earth atoms that have been proposed for experiments on Rydberg-Rydberg interactions. For the rare-earth atoms, the core electrons can have a very substantial total angular momentum J and a nonzero nuclear spin I . In the alkaline-earth atoms there is a single (s ) core electron whose spin can couple to a nonzero nuclear spin for odd isotopes. The resulting hyperfine splitting of the core state can lead to substantial mixing between the Rydberg series attached to different thresholds. Compared to the unperturbed Rydberg series of the alkali-metal atoms, the series perturbations and near degeneracies from the different parity states could lead to qualitatively different behavior for single-atom Rydberg properties (polarizability, Zeeman mixing and splitting, etc.) as well as Rydberg-Rydberg interactions (C5 and C6 matrices).

Hyperfine field, electric field gradient, quadrupole coupling constant and magnetic properties of challenging actinide digallide

NASA Astrophysics Data System (ADS)

Khan, Sajid; Yazdani-Kachoei, M.; Jalali-Asadabadi, S.; Ahmad, Iftikhar

2017-12-01

In this paper, we explore the structural and magnetic properties as well as electric field gradient (EFG), hyperfine field (HFF) and quadrupole coupling constant in actinide digallide AcGa2 (Ac = U, Np, Pu) using LDA, GGA, LDA+U, GGA+U and hybrid functional with Wu-Cohen Generalized Gradient approximation HF-WC. Relativistic effects of the electrons are considered by including spin-orbit coupling. The comparison of the calculated structural parameters and magnetic properties with the available experimental results confirms the consistency and hence effectiveness of our theoretical tools. The calculated magnetic moments demonstrate that UGa2 and NpGa2 are ferromagnetic while PuGa2 is antiferromagnetic in nature. The EFG of AcGa2 is reported for the first time. The HFF, EFG and quadrupole coupling constant in AcGa2 (Ac = U, Np, Pu) are mainly originated from f-f and p-p contributions of Ac atom and p-p contribution of Ga atom.

Matrix elements of hyperfine structure operators in the SL and jj representations for the s, p{sup N}, and d{sup N} configurations and the SL-jj transformation

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

Childs, W.J.

1997-09-01

Matrix elements of the hyperfine operators corresponding to the magnetic-dipole (A) and electric-quadrupole (B) hyperfine structures constants are given as linear combinations of the appropriate radial integrals for all states of the s, p{sup N}, and d{sub N} configurations in both the SL and pure jj representations. The associated SL-jj transformations are also given. 13 refs., 10 tabs.

EPR study of free radical in gamma-irradiated bis(cyclopentadienyl)zirconium dichloride single crystal

NASA Astrophysics Data System (ADS)

Caliskan, Betul; Caliskan, Ali Cengiz

2017-06-01

Bis(cyclopentadienyl)zirconium dichloride (BCZD; zirconocene dichloride) single crystals were exposed to 60Co-γ irradiation at room temperature. The irradiated single crystals were investigated between 125 and 470 K by electron paramagnetic resonance spectroscopy. The spectra of the crystals were found to be temperature independent. The paramagnetic center was attributed to the cyclopentadienyl radical. The g values of the radiation damage center observed in BCZD single crystal and the hyperfine structure constants of the free electron with nearby protons were obtained.

Structure of Radicals from X-irradiated Guanine Derivatives: An Experimental and Computational Study of Sodium Guanosine Dihydrate Single Crystals

PubMed Central

Jayatilaka, Nayana; Nelson, William H.

2008-01-01

In sodium guanosine dihydrate single crystals, the guanine moiety is deprotonated at N1 due to growth from high-pH (>12) solutions. EPR and ENDOR study of crystals x-irradiated at 10 K detected evidence for three radical forms. Radical R1,characterized by two proton and two nitrogen hyperfine interactions, was identified as the product of net hydrogenation at N7 of the N1-deprotonated guanine unit. R1 exhibited an unusually distorted structure leading to net positive isotropic components of the hydrogen couplings. Radical R2, characterized by one proton and one nitrogen hyperfine coupling was identified as the primary electron loss product. This product is equivalent to that of deprotonation at N1 by the guanine cation and represents the first ENDOR characterization of that product. Radical R3, characterized by a single hydrogen hyperfine coupling, was identified as the product of net dehydrogenation at C1 of the ribose moiety. The identification of radicals R1-R3 was supported by DFT calculations on several possible structures using the B3LYP/6-311G(2df,p)//6-31G(d,p) approach. Radical R4, detected after warming the crystals to room temperature, was identified as the well-known product of net hydrogenation of C8 of the (N1-deprotonated) guanine component. Radical R1, evidently formed by protonation of the primary electron addition product, was present as roughly 60% of the total radicals detected at 10 K. Radical R2 was present as roughly 27% of the total yield, and the concentration of R3 contributed the remaining 13%. R3 is evidently the product of oneelectron oxidation followed by deprotonation; thus, the balance of oxidation and reduction products is approximately equal within experimental uncertainty. PMID:17249824

Fourier transform millimeter-wave spectroscopy of the ethyl radical in the electronic ground state.

PubMed

Kim, Eunsook; Yamamoto, Satoshi

2004-02-15

The pure rotational spectrum of the ethyl radical (C2H5) has been detected for the first time with the Fourier transform millimeter-wave spectrometer. The ethyl radical is produced by discharging the C2H5I gas diluted in Ar. The 1(01)-0(00) rotational transition of the ethyl radical is observed in the frequency range from 43,680 to 43,780 MHz. The observed spectrum shows a very complicated pattern of the fine and hyperfine structures of a doublet radical with the nuclear spins of five protons. The fine and hyperfine components are assigned with the aid of measurements of the Zeeman splittings. As a result, the 22 lines are ascribed to the transitions in the ground vibronic state (A2"). The rotational constant, the spin-rotation interaction constant, and hyperfine interaction constants are determined by the least-squares fit. The Fermi contact term of the alpha-proton is determined to be -64.1654 MHz in the gas phase, indicating that the structure of the -CH2 is essentially planar. The present rotational spectroscopic study further supports that the methyl group of the ethyl radical can be regarded as a nearly free internal rotor with a low energy barrier. A few unassigned lines still remain, which may be vibrational satellites of the internal rotation mode. Copyright 2004 American Institute of Physics

Isotropic Inelastic Collisions in a Multiterm Atom with Hyperfine Structure

NASA Astrophysics Data System (ADS)

Belluzzi, Luca; Landi Degl'Innocenti, Egidio; Trujillo Bueno, Javier

2015-10-01

A correct modeling of the scattering polarization profiles observed in some spectral lines of diagnostic interest, the sodium doublet being one of the most important examples, requires taking hyperfine structure (HFS) and quantum interference between different J-levels into account. An atomic model suitable for taking these physical ingredients into account is the so-called multiterm atom with HFS. In this work, we introduce and study the transfer and relaxation rates due to isotropic inelastic collisions with electrons, which enter the statistical equilibrium equations (SEE) for the atomic density matrix of this atomic model. Under the hypothesis that the electron-atom interaction is described by a dipolar operator, we provide useful relations between the rates describing the transfer and relaxation of quantum interference between different levels (whose numerical values are in most cases unknown) and the usual rates for the atomic level populations, for which experimental data and/or approximate theoretical expressions are generally available. For the particular case of a two-term atom with HFS, we present an analytical solution of the SEE for the spherical statistical tensors of the upper term, including both radiative and collisional processes, and we derive the expression of the emission coefficient in the four Stokes parameters. Finally, an illustrative application to the Na i D1 and D2 lines is presented.

Hyperfine Structure Constants of Energetically High-lying Levels of Odd Parity of Atomic Vanadium

NASA Astrophysics Data System (ADS)

Güzelçimen, F.; Yapıcı, B.; Demir, G.; Er, A.; Öztürk, I. K.; Başar, Gö.; Kröger, S.; Tamanis, M.; Ferber, R.; Docenko, D.; Başar, Gü.

2014-09-01

High-resolution Fourier transform spectra of a vanadium-argon plasma have been recorded in the wavelength range of 365-670 nm (15,000-27,400 cm-1). Optical bandpass filters were used in the experimental setup to enhance the sensitivity of the Fourier transform spectrometer. In total, 138 atomic vanadium spectral lines showing resolved or partially resolved hyperfine structure have been analyzed to determine the magnetic dipole hyperfine structure constants A of the involved energy levels. One of the investigated lines has not been previously classified. As a result, the magnetic dipole hyperfine structure constants A for 90 energy levels are presented: 35 of them belong to the configuration 3d 34s4p and 55 to the configuration 3d 44p. Of these 90 constants, 67 have been determined for the first time, with 23 corresponding to the configuration 3d 34s4p and 44 to 3d 44p.

Construction of the energy matrix for complex atoms. Part VIII: Hyperfine structure HPC calculations for terbium atom

NASA Astrophysics Data System (ADS)

Elantkowska, Magdalena; Ruczkowski, Jarosław; Sikorski, Andrzej; Dembczyński, Jerzy

2017-11-01

A parametric analysis of the hyperfine structure (hfs) for the even parity configurations of atomic terbium (Tb I) is presented in this work. We introduce the complete set of 4fN-core states in our high-performance computing (HPC) calculations. For calculations of the huge hyperfine structure matrix, requiring approximately 5000 hours when run on a single CPU, we propose the methods utilizing a personal computer cluster or, alternatively a cluster of Microsoft Azure virtual machines (VM). These methods give a factor 12 performance boost, enabling the calculations to complete in an acceptable time.

Hyperfine structure investigations for the odd-parity configuration system in atomic holmium

NASA Astrophysics Data System (ADS)

Stefanska, D.; Furmann, B.

2018-02-01

In this work new experimental results of the hyperfine structure (hfs) in the holmium atom are reported, concerning the odd-parity level system. Investigations were performed by the method of laser induced fluorescence in a hollow cathode discharge lamp on 97 spectral lines in the visible part of the spectrum. Hyperfine structure constants: magnetic dipole - A and electric quadrupole - B for 40 levels were determined for the first time; for another 21 levels the hfs constants available in the literature were remeasured. Results for the A constants can be viewed as fully reliable; for B constants further possibilities of improving the accuracy are considered.

Molecules in high spin states III: The millimeter/submillimeter-wave spectrum of the MnCl radical (X 7Σ+)

NASA Astrophysics Data System (ADS)

Halfen, D. T.; Ziurys, L. M.

2005-02-01

The pure rotational spectrum of the MnCl radical (X 7Σ+) has been recorded in the range 141-535 GHz using millimeter-submillimeter direct absorption spectroscopy. This work is the first time the molecule has been studied with rotational resolution in its ground electronic state. MnCl was synthesized by the reaction of manganese vapor, produced in a Broida-type oven, with Cl2. Transitions of both chlorine isotopomers were measured, as well as lines originating in several vibrationally excited states. The presence of several spin components and manganese hyperfine interactions resulted in quite complex spectra, consisting of multiple blended features. Because 42 rotational transitions were measured for Mn35Cl over a wide range of frequencies with high signal-to-noise, a very accurate set of rotational, fine structure, and hyperfine constants could be determined with the aid of spectral simulations. Spectroscopic constants were also determined for Mn37Cl and several vibrationally excited states. The values of the spin-rotation and spin-spin parameters were found to be relatively small (γ=11.2658 MHz and λ=1113.10 MHz for Mn35Cl); in the case of λ, excited electronic states contributing to the second-order spin-orbit interaction may be canceling each other. The Fermi contact hyperfine term was found to be large in manganese chloride with bF(Mn35Cl)=397.71 MHz, a result of the manganese 4s character mixing into the 12σ orbital. This orbital is spσ hybridized, and contains some Mn 4pσ character, as well. Hence, it also contributes to the dipolar constant c, which is small and positive for this radical (c=32.35 MHz for Mn35Cl). The hyperfine parameters in MnCl are similar to those of MnH and MnF, suggesting that the bonding in these three molecules is comparable.

Molecules in high spin states III: the millimeter/submillimeter-wave spectrum of the MnCl radical (X (7)Sigma(+)).

PubMed

Halfen, D T; Ziurys, L M

2005-02-01

The pure rotational spectrum of the MnCl radical (X (7)Sigma(+)) has been recorded in the range 141-535 GHz using millimeter-submillimeter direct absorption spectroscopy. This work is the first time the molecule has been studied with rotational resolution in its ground electronic state. MnCl was synthesized by the reaction of manganese vapor, produced in a Broida-type oven, with Cl(2). Transitions of both chlorine isotopomers were measured, as well as lines originating in several vibrationally excited states. The presence of several spin components and manganese hyperfine interactions resulted in quite complex spectra, consisting of multiple blended features. Because 42 rotational transitions were measured for Mn(35)Cl over a wide range of frequencies with high signal-to-noise, a very accurate set of rotational, fine structure, and hyperfine constants could be determined with the aid of spectral simulations. Spectroscopic constants were also determined for Mn(37)Cl and several vibrationally excited states. The values of the spin-rotation and spin-spin parameters were found to be relatively small (gamma=11.2658 MHz and lambda=1113.10 MHz for Mn(35)Cl); in the case of lambda, excited electronic states contributing to the second-order spin-orbit interaction may be canceling each other. The Fermi contact hyperfine term was found to be large in manganese chloride with b(F)(Mn(35)Cl)=397.71 MHz, a result of the manganese 4s character mixing into the 12sigma orbital. This orbital is spsigma hybridized, and contains some Mn 4psigma character, as well. Hence, it also contributes to the dipolar constant c, which is small and positive for this radical (c=32.35 MHz for Mn(35)Cl). The hyperfine parameters in MnCl are similar to those of MnH and MnF, suggesting that the bonding in these three molecules is comparable.

Full hyperfine structure analysis of singly ionized molybdenum

NASA Astrophysics Data System (ADS)

Bouazza, Safa

2017-03-01

For a first time a parametric study of hyperfine structure of Mo II configuration levels is presented. The newly measured A and B hyperfine structure (hfs) constants values of Mo II 4d5, 4d45s and 4d35s2 configuration levels, for both 95 and 97 isotopes, using Fast-ion-beam laser-induced fluorescence spectroscopy [1] are gathered with other few data available in literature. A fitting procedure of an isolated set of these three lowest even-parity configuration levels has been performed by taking into account second-order of perturbation theory including the effects of closed shell-open shell excitations. Moreover the same study was done for Mo II odd-parity levels; for both parities two sets of fine structure parameters as well as the leading eigenvector percentages of levels and Landé-factor gJ, relevant for this paper are given. We present also predicted singlet, triplet and quintet positions of missing experimental levels up to 85000 cm-1. The single-electron hfs parameter values were extracted in their entirety for 97Mo II and for 95Mo II: for instance for 95Mo II, a4d 01 =-133.37 MHz and a5p 01 =-160.25 MHz for 4d45p; a4d 01 =-140.84 MHz, a5p 01 =-170.18 MHz and a5s 10 =-2898 MHz for 4d35s5p; a5s 10 =-2529 (2) MHz and a4d 01 =-135.17 (0.44) MHz for the 4d45s. These parameter values were analysed and compared with diverse ab-initio calculations. We closed this work with giving predicted values of magnetic dipole and electric quadrupole hfs constants of all known levels, whose splitting are not yet measured.

One-electron oxidation of individual DNA bases and DNA base stacks.

PubMed

Close, David M

2010-02-04

In calculations performed with DFT there is a tendency of the purine cation to be delocalized over several bases in the stack. Attempts have been made to see if methods other than DFT can be used to calculate localized cations in stacks of purines, and to relate the calculated hyperfine couplings with known experimental results. To calculate reliable hyperfine couplings it is necessary to have an adequate description of spin polarization which means that electron correlation must be treated properly. UMP2 theory has been shown to be unreliable in estimating spin densities due to overestimates of the doubles correction. Therefore attempts have been made to use quadratic configuration interaction (UQCISD) methods to treat electron correlation. Calculations on the individual DNA bases are presented to show that with UQCISD methods it is possible to calculate hyperfine couplings in good agreement with the experimental results. However these UQCISD calculations are far more time-consuming than DFT calculations. Calculations are then extended to two stacked guanine bases. Preliminary calculations with UMP2 or UQCISD theory on two stacked guanines lead to a cation localized on a single guanine base.

Local structure study of Fe dopants in Ni-deficit Ni 3Al alloys

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

V. N. Ivanovski; Umicevic, A.; Belosevic-Cavor, J.

2015-08-24

We found that the local electronic and magnetic structure, hyperfine interactions, and phase composition of polycrystalline Ni–deficient Ni 3-x FexAl (x = 0.18 and 0.36) were investigated by means of 57 Fe Mössbauer spectroscopy. The samples were characterized by X–ray diffraction and magnetization measurements. The ab initio calculations performed with the projector augmented wave method and the calculations of the energies of iron point defects were done to elucidate the electronic structure and site preference of Fe doped Ni 3 Al. Moreover, the value of calculated electric field gradient tensor V zz=1.6 10 21Vm -2 matches well with the resultsmore » of Mössbauer spectroscopy and indicates that the Fe atoms occupy Ni sites.« less

Spin relaxation in quantum dots due to electron exchange with leads.

PubMed

Vorontsov, A B; Vavilov, M G

2008-11-28

We calculate spin relaxation rates in lateral quantum dot systems due to electron exchange between dots and leads. Using rate equations, we develop a theoretical description of the experimentally observed electric current in the spin blockade regime of double quantum dots. A single expression fits the entire current profile and describes the structure of both the conduction peaks and the suppressed ("valley") region. Extrinsic rates calculated here have to be taken into account for accurate extraction of intrinsic relaxation rates due to the spin-orbit and hyperfine spin scattering mechanisms from spin blockade measurements.

Electron Magnetic Resonance of X-Irradiated Potassium Hydrogen Maleate

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

Heller, H. C.; Cole, T.

1962-12-01

X irradiation of a single crystal of potassium hydrogen maleate HOOCCH = CHCOOK was found to produce a free radical in which the unpaired electron interacts with only two protons. The electron magnetic resonance of this radical, shown to be OOCCH = CHCOO-, indicates that it is oriented in the host crystal in the same way as the parent hydrogen maleate ion. The principal values of the proton hyperfine tensors of the radical are; -19.0, -28.4, and -8.0 Mc. The rather small principal values and their directions indicate that the unpaired electron in the radical is in a p pimore » orbital delocalized over the whole radical, including the carboxyl groupa. The directions of the principal values are in agreement with the cis-structure of the parent molecule. The utilization of emr spectra in differentiating between cis- and trans-structures of radicals is briefly discussed.« less

Radiation effects in x-irradiated hydroxy compounds

NASA Astrophysics Data System (ADS)

Budzinski, Edwin E.; Potter, William R.; Box, Harold C.

1980-01-01

Radiation effects are compared in single crystals of xylitol, sorbitol, and dulcitol x-irradiated at 4.2 °K. In xylitol and dulcitol, but not in sorbitol, a primary oxidation product is identified as an alkoxy radical. ENDOR measurements detected three proton hyperfine couplings associated with the alkoxy ESR absorption, one of which is attributed to a proton three bond lengths removed from the seat of unpaired spin density. Intermolecular trapping of electrons is observed in all three crystals. ENDOR measurements were made of the hyperfine couplings between the trapped electron and the hydroxy protons forming the trap.

Nonlocal Polarization Feedback in a Fractional Quantum Hall Ferromagnet.

PubMed

Hennel, Szymon; Braem, Beat A; Baer, Stephan; Tiemann, Lars; Sohi, Pirouz; Wehrli, Dominik; Hofmann, Andrea; Reichl, Christian; Wegscheider, Werner; Rössler, Clemens; Ihn, Thomas; Ensslin, Klaus; Rudner, Mark S; Rosenow, Bernd

2016-04-01

In a quantum Hall ferromagnet, the spin polarization of the two-dimensional electron system can be dynamically transferred to nuclear spins in its vicinity through the hyperfine interaction. The resulting nuclear field typically acts back locally, modifying the local electronic Zeeman energy. Here we report a nonlocal effect arising from the interplay between nuclear polarization and the spatial structure of electronic domains in a ν=2/3 fractional quantum Hall state. In our experiments, we use a quantum point contact to locally control and probe the domain structure of different spin configurations emerging at the spin phase transition. Feedback between nuclear and electronic degrees of freedom gives rise to memristive behavior, where electronic transport through the quantum point contact depends on the history of current flow. We propose a model for this effect which suggests a novel route to studying edge states in fractional quantum Hall systems and may account for so-far unexplained oscillatory electronic-transport features observed in previous studies.

Quadrupole splittings in the near-infrared spectrum of 14NH 3

DOE PAGES

Twagirayezu, Sylvestre; Hall, Gregory E.; Sears, Trevor J.

2016-10-13

Sub-Doppler, saturation dip, spectra of lines in the v 1 + v 3, v 1 + 2v 4 and v 3 + 2v 4 bands of 14NH 3 have been measured by frequency comb-referenced diode laser absorption spectroscopy. The observed spectral line widths are dominated by transit time broadening, and show resolved or partially-resolved hyperfine splittings that are primarily determined by the 14N quadrupole coupling. Modeling of the observed line shapes based on the known hyperfine level structure of the ground state of the molecule shows that, in nearly all cases, the excited state level has hyperfine splittings similar tomore » the same rotational level in the ground state. The data provide accurate frequencies for the line positions and easily separate lines overlapped in Doppler-limited spectra. The observed hyperfine splittings can be used to make and confirm rotational assignments and ground state combination differences obtained from the measured frequencies are comparable in accuracy to those obtained from conventional microwave spectroscopy. Furthermore, several of the measured transitions do not show the quadrupole hyperfine splittings expected based on their existing rotational assignments. Either the assignments are incorrect or the upper levels involved are perturbed in a way that affects the nuclear hyperfine structure.« less

Revised energy levels of singly ionized lanthanum

NASA Astrophysics Data System (ADS)

Güzelçimen, Feyza; Tonka, Mehdi; Uddin, Zaheer; Bhatti, Naveed Anjum; Windholz, Laurentius; Kröger, Sophie; Başar, Gönül

2018-05-01

Based on the experimental wavenumbers of 344 spectral lines from calibrated Fourier transform (FT) spectra as well as wavenumbers of 81 lines from the wavelength tables from literature, the energy of 115 fine structure levels of singly ionized lanthanum has been revised by weighted global fits. The classifications of the lines are provided by numerous previous investigations of lanthanum by different spectroscopic methods and authors. For the high accurate determination of the center of gravity wavenumbers from the experimental spectrum, the hyperfine constants of the involved levels have been taken into account, if possible. For the 94 levels with known hyperfine constants the accuracy of energy values is better than 0.01 cm-1. For 34 levels the magnetic dipole hyperfine constants A have been determined from FT spectra as part of this work. For four of these 34 levels even electric quadrupole hyperfine constants B could be estimated. For levels, which have experimentally unknown hyperfine constants and which are connected only by lines not found in the FT spectra but taken from literature, the uncertainties of energy values are about a factor of 10 higher. A list of all revised level energies together with a compilation of hyperfine structure data is given as well as a list of all lines used.

Using Hyperfine Structure to Quantify the Effects of Substitution on the Electron Distribution Within a Pyridine Ring: a Study of 2-, 3-, and 4-PICOLYLAMINE

NASA Astrophysics Data System (ADS)

McDivitt, Lindsey M.; Himes, Korrina M.; Bailey, Josiah R.; McMahon, Timothy J.; Bird, Ryan G.

2017-06-01

The ground state rotational spectra of the three methylamine substituted pyridines, 2-, 3-, and 4-picolylamine, were collected and analyzed over the frequency range of 7-17.5 GHz using chirped-pulsed Fourier transform microwave spectroscopy. All three molecules show a distinctive quadrupole splitting, which is representative of the local electronic environment around the two different ^{14}N nuclei, with the pyridine nitrogen being particularly sensitive to the pi-electron distribution within the ring. The role that the position of the methylamine group plays on the quadrupole coupling constants on both nitrogens will be discussed and compared to other substituted pyridines.

Magnetic properties and hyperfine interactions in Cr{sub 8}, Cr{sub 7}Cd, and Cr{sub 7}Ni molecular rings from {sup 19}F-NMR

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

Bordonali, L.; Borsa, F.; Consorzio INSTM, Via Giusti 9, I-50121 Firenze

2014-04-14

A detailed experimental investigation of the {sup 19}F nuclear magnetic resonance is made on single crystals of the homometallic Cr{sub 8} antiferromagnetic molecular ring and heterometallic Cr{sub 7}Cd and Cr{sub 7}Ni rings in the low temperature ground state. Since the F{sup −} ion is located midway between neighboring magnetic metal ions in the ring, the {sup 19}F-NMR spectra yield information about the local electronic spin density and {sup 19}F hyperfine interactions. In Cr{sub 8}, where the ground state is a singlet with total spin S{sub T} = 0, the {sup 19}F-NMR spectra at 1.7 K and low external magnetic fieldmore » display a single narrow line, while when the magnetic field is increased towards the first level crossing field, satellite lines appear in the {sup 19}F-NMR spectrum, indicating a progressive increase in the Boltzmann population of the first excited state S{sub T} = 1. In the heterometallic rings, Cr{sub 7}Cd and Cr{sub 7}Ni, whose ground state is magnetic with S{sub T} = 3/2 and S{sub T} = 1/2, respectively, the {sup 19}F-NMR spectrum has a complicated structure which depends on the strength and orientation of the magnetic field, due to both isotropic and anisotropic transferred hyperfine interactions and classical dipolar interactions. From the {sup 19}F-NMR spectra in single crystals we estimated the transferred hyperfine constants for both the F{sup −}-Ni{sup 2+} and the F{sup −}-Cd{sup 2+} bonds. The values of the hyperfine constants compare well to the ones known for F{sup −}-Ni{sup 2+} in KNiF{sub 3} and NiF{sub 2} and for F{sup −}-Cr{sup 3+} in K{sub 2}NaCrF{sub 6}. The results are discussed in terms of hybridization of the 2s, 2p orbitals of the F{sup −} ion and the d orbitals of the magnetic ion. Finally, we discuss the implications of our results for the electron-spin decoherence.« less

Materials for optical memory: Resolved hyperfine structure in KY3F10:Ho3+

NASA Astrophysics Data System (ADS)

Popova, M. N.

2013-08-01

Basic principles of creating a quantum optical memory (QOM) and requirements for relevant materials, in particular, for crystals doped with rare-earth ions, are briefly reviewed. A combined approach to studying the hyperfine structure, which is essential for QOM applications, is presented on the example of KY3F10:Ho3+.

Theoretical study of the hyperfine-interaction constants and the isotope-shift factors for the 3 s21S0-3 s 3 p 3,1P1o transitions in Al+

NASA Astrophysics Data System (ADS)

Zhang, Tingxian; Xie, Luyou; Li, Jiguang; Lu, Zehuang

2017-07-01

We calculated the magnetic dipole and the electric quadrupole hyperfine interaction constants of 3 s 3 p 3,1P1o states and the isotope shift, including mass and field shift, factors for transitions from these two states to the ground state 3 s 2 1S0 in Al+ ions using the multiconfiguration Dirac-Hartree-Fock method. The effects of the electron correlations and the Breit interaction on these physical quantities were investigated in detail based on the active space approach. It is found that the core-core and the higher order correlations are considerable for evaluating the uncertainties of the atomic parameters concerned. The uncertainties of the hyperfine interaction constants in this work are less than 1.6%. Although the isotope shift factors are highly sensitive to the electron correlations, reasonable uncertainties were obtained by exploring the effects of the electron correlations. Moreover, we found that the relativistic nuclear recoil corrections to the mass shift factors are very small and insensitive to the electron correlations for Al+. These atomic parameters present in this work are valuable for extracting the nuclear electric quadrupole moments and the mean-square charge radii of Al isotopes.

Conformational control of cofactors in nature: The effect of methoxy group orientation on the electronic structure of ubisemiquinone

NASA Astrophysics Data System (ADS)

De Almeida, Wagner B.; O'Malley, Patrick J.

2018-03-01

Ubiquinone is the key electron and proton transfer agent in biology. Its mechanism involves the formation of its intermediate one-electron reduced form, the ubisemiquinone radical. This is formed in a protein-bound form which permits the semiquinone to vary its electronic and redox properties. This can be achieved by hydrogen bonding acceptance by one or both oxygen atoms or as we now propose by restricted orientations for the methoxy groups of the headgroup. We show how the orientation of the two methoxy groups of the quinone headgroup affects the electronic structure of the semiquinone form and demonstrate a large dependence of the ubisemiquinone spin density distribution on the orientation each methoxy group takes with respect to the headgroup ring plane. This is shown to significantly modify associated hyperfine couplings which in turn needs to be accounted for in interpreting experimental values in vivo. The study uncovers the key potential role the methoxy group orientation can play in controlling the electronic structure and spin density of ubisemiquinone and provides an electronic-level insight into the variation in electron affinity and redox potential of ubiquinone as a function of the methoxy orientation. Taken together with the already known influence of cofactor conformation on heme and chlorophyll electronic structure, it reveals a more widespread role for cofactor conformational control of electronic structure and associated electron transfer in biology.

Observation of the hyperfine spectrum of antihydrogen.

PubMed

Ahmadi, M; Alves, B X R; Baker, C J; Bertsche, W; Butler, E; Capra, A; Carruth, C; Cesar, C L; Charlton, M; Cohen, S; Collister, R; Eriksson, S; Evans, A; Evetts, N; Fajans, J; Friesen, T; Fujiwara, M C; Gill, D R; Gutierrez, A; Hangst, J S; Hardy, W N; Hayden, M E; Isaac, C A; Ishida, A; Johnson, M A; Jones, S A; Jonsell, S; Kurchaninov, L; Madsen, N; Mathers, M; Maxwell, D; McKenna, J T K; Menary, S; Michan, J M; Momose, T; Munich, J J; Nolan, P; Olchanski, K; Olin, A; Pusa, P; Rasmussen, C Ø; Robicheaux, F; Sacramento, R L; Sameed, M; Sarid, E; Silveira, D M; Stracka, S; Stutter, G; So, C; Tharp, T D; Thompson, J E; Thompson, R I; van der Werf, D P; Wurtele, J S

2017-08-02

The observation of hyperfine structure in atomic hydrogen by Rabi and co-workers and the measurement of the zero-field ground-state splitting at the level of seven parts in 10 13 are important achievements of mid-twentieth-century physics. The work that led to these achievements also provided the first evidence for the anomalous magnetic moment of the electron, inspired Schwinger's relativistic theory of quantum electrodynamics and gave rise to the hydrogen maser, which is a critical component of modern navigation, geo-positioning and very-long-baseline interferometry systems. Research at the Antiproton Decelerator at CERN by the ALPHA collaboration extends these enquiries into the antimatter sector. Recently, tools have been developed that enable studies of the hyperfine structure of antihydrogen-the antimatter counterpart of hydrogen. The goal of such studies is to search for any differences that might exist between this archetypal pair of atoms, and thereby to test the fundamental principles on which quantum field theory is constructed. Magnetic trapping of antihydrogen atoms provides a means of studying them by combining electromagnetic interaction with detection techniques that are unique to antimatter. Here we report the results of a microwave spectroscopy experiment in which we probe the response of antihydrogen over a controlled range of frequencies. The data reveal clear and distinct signatures of two allowed transitions, from which we obtain a direct, magnetic-field-independent measurement of the hyperfine splitting. From a set of trials involving 194 detected atoms, we determine a splitting of 1,420.4 ± 0.5 megahertz, consistent with expectations for atomic hydrogen at the level of four parts in 10 4 . This observation of the detailed behaviour of a quantum transition in an atom of antihydrogen exemplifies tests of fundamental symmetries such as charge-parity-time in antimatter, and the techniques developed here will enable more-precise such tests.

Observation of the hyperfine spectrum of antihydrogen

NASA Astrophysics Data System (ADS)

Ahmadi, M.; Alves, B. X. R.; Baker, C. J.; Bertsche, W.; Butler, E.; Capra, A.; Carruth, C.; Cesar, C. L.; Charlton, M.; Cohen, S.; Collister, R.; Eriksson, S.; Evans, A.; Evetts, N.; Fajans, J.; Friesen, T.; Fujiwara, M. C.; Gill, D. R.; Gutierrez, A.; Hangst, J. S.; Hardy, W. N.; Hayden, M. E.; Isaac, C. A.; Ishida, A.; Johnson, M. A.; Jones, S. A.; Jonsell, S.; Kurchaninov, L.; Madsen, N.; Mathers, M.; Maxwell, D.; McKenna, J. T. K.; Menary, S.; Michan, J. M.; Momose, T.; Munich, J. J.; Nolan, P.; Olchanski, K.; Olin, A.; Pusa, P.; Rasmussen, C. Ø.; Robicheaux, F.; Sacramento, R. L.; Sameed, M.; Sarid, E.; Silveira, D. M.; Stracka, S.; Stutter, G.; So, C.; Tharp, T. D.; Thompson, J. E.; Thompson, R. I.; van der Werf, D. P.; Wurtele, J. S.

2017-08-01

The observation of hyperfine structure in atomic hydrogen by Rabi and co-workers and the measurement of the zero-field ground-state splitting at the level of seven parts in 1013 are important achievements of mid-twentieth-century physics. The work that led to these achievements also provided the first evidence for the anomalous magnetic moment of the electron, inspired Schwinger’s relativistic theory of quantum electrodynamics and gave rise to the hydrogen maser, which is a critical component of modern navigation, geo-positioning and very-long-baseline interferometry systems. Research at the Antiproton Decelerator at CERN by the ALPHA collaboration extends these enquiries into the antimatter sector. Recently, tools have been developed that enable studies of the hyperfine structure of antihydrogen—the antimatter counterpart of hydrogen. The goal of such studies is to search for any differences that might exist between this archetypal pair of atoms, and thereby to test the fundamental principles on which quantum field theory is constructed. Magnetic trapping of antihydrogen atoms provides a means of studying them by combining electromagnetic interaction with detection techniques that are unique to antimatter. Here we report the results of a microwave spectroscopy experiment in which we probe the response of antihydrogen over a controlled range of frequencies. The data reveal clear and distinct signatures of two allowed transitions, from which we obtain a direct, magnetic-field-independent measurement of the hyperfine splitting. From a set of trials involving 194 detected atoms, we determine a splitting of 1,420.4 ± 0.5 megahertz, consistent with expectations for atomic hydrogen at the level of four parts in 104. This observation of the detailed behaviour of a quantum transition in an atom of antihydrogen exemplifies tests of fundamental symmetries such as charge-parity-time in antimatter, and the techniques developed here will enable more-precise such tests.

Hyperfine interaction mechanism of magnetic field effects in sequential fluorophore and exciplex fluorescence.

PubMed

Dodin, Dmitry V; Ivanov, Anatoly I; Burshtein, Anatoly I

2013-03-28

The magnetic field effect on the fluorescence of the photoexcited electron acceptor, (1)A∗, and the exciplex, (1)[D(+δ)A(-δ)] formed at contact of (1)A∗ with an electron donor (1)D, is theoretically explored in the framework of Integral Encounter Theory. It is assumed that the excited fluorophore is equilibrated with the exciplex that reversibly dissociates into the radical-ion pair. The magnetic field sensitive stage is the spin conversion in the resulting geminate radical-ion pair, (1, 3)[D(+)...A(-)] that proceeds due to hyperfine interaction. We confirm our earlier conclusion (obtained with a rate description of spin conversion) that in the model with a single nucleus spin 1/2 the magnitude of the Magnetic Field Effect (MFE) also vanishes in the opposite limits of low and high dielectric permittivity of the solvent. Moreover, it is shown that MFE being positive at small hyperfine interaction A, first increases with A but approaching the maximum starts to decrease and even changes the sign.

HYPERFINE-DEPENDENT gf-VALUES OF Mn I LINES IN THE 1.49-1.80 μm H BAND

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

Andersson, M.; Hutton, R.; Zou, Y.

2015-01-01

The three Mn I lines at 17325, 17339, and 17349 Å are among the 25 strongest lines (log (gf) > 0.5) in the H band. They are all heavily broadened due to hyperfine structure, and the profiles of these lines have so far not been understood. Earlier studies of these lines even suggested that they were blended. In this work, the profiles of these three infrared (IR) lines have been studied theoretically and compared to experimental spectra to assist in the complete understanding of the solar spectrum in the IR. It is shown that the structure of these lines cannot be describedmore » in the conventional way using the diagonal A and B hyperfine interaction constants. The off-diagonal hyperfine interaction not only has a large impact on the energies of the hyperfine levels, but also introduces a large intensity redistribution among the hyperfine lines, changing the line profiles dramatically. By performing large-scale calculations of the diagonal and off-diagonal hyperfine interaction and the gf-values between the upper and lower hyperfine levels and using a semi-empirical fitting procedure, we achieved agreement between our synthetic and experimental spectra. Furthermore, we compare our results with observations of stellar spectra. The spectra of the Sun and the K1.5 III red giant star Arcturus were modeled in the relevant region, 1.73-1.74 μm, using our theoretically predicted gf-values and energies for each individual hyperfine line. Satisfactory fits were obtained and clear improvements were found using our new data compared with the old available Mn I data. A complete list of energies and gf-values for all the 3d {sup 5}4s({sup 7} S)4d e{sup 6}D - 3d {sup 5}4s({sup 7} S)4f w{sup 6}F hyperfine lines are available as supporting material, whereas only the stronger lines are presented and discussed in detail in this paper.« less

Studies of molecular physics in sodium-potassium: An analysis of the 4(3)Sigma+ state and interactions between the 2(A)(1)Sigma+ and 1(b)(3)Pi states

NASA Astrophysics Data System (ADS)

Burns, Patrick

2004-12-01

In this dissertation we report the results of three experiments designed to provide new information on the structure and interactions of the NaK molecule. Specifically these experiments investigate 2(A)1Sigma +(upsilonA, J) + M → 1(b)3 pi0(upsilonb, J) + M collisional excitation transfers (where M is a collision partner), hyperfine structure of the NaK 1(b)3pi and 1(b)3pi0 ˜ 2(A)1Sigma+ spin-orbit interactions, and the structure and spectra of the NaK 43Sigma+ state, respectively. In this first experiment, populations of collisionally populated levels were recorded near the NaK 1(b)3pi0(upsilon =18, J = 44) ˜ 2(A)1Sigma+ (upsilon = 20, J = 44) center of spin-orbit perturbation. Our data indicate that population is transferred from the pumped level, 2(A) 1Sigma+(upsilon = 20, J = 49), directly to the surrounding "daughter" levels [1(b)3Sigma 0(upsilon =18, J = 45--48) and 2(A)1Sigma +(upsilon = 20, J = 45--48)]. The relative populations of the daughter levels appear anomalous, as their populations do not monotonically decrease for levels further away in energy from the pumped level. We have measured the hyperfine structure of mutually perturbing ro-vibrational levels of the 1(b)3pi0 and 2(A)1Sigma + states of the NaK molecule, using the PFOODR method with co-propagating lasers. Unperturbed 1(b)3pi0 levels are split into four hyperfine components by the Fermi contact interaction b FI·S. Mixing between the 1(b)3pi0 and 2(A)1Sigma + levels imparts hyperfine structure to the nominally singlet component, and reduces the hyperfine splitting of the nominally triplet component, of the perturbed levels. We determined a value for the Fermi constant, bF= (0.00989 +/- 0.00027) cm-1, and the magnitude of the electronic part of the 1(b)3pi 0 ˜ 2(A)1Sigma+ spin-orbit coupling, |Hel| = (15.65 +/- 0.14) cm-1 , from an analysis of the measured hyperfine splittings of the mixed singlet-triplet levels. High-resolution spectra have been observed for numerous vibrational-rotational levels (upsilon, N) of the 43Sigma + state of NaK. A potential curve was obtained from the data using the inverse perturbation approximation method. Measured bound-free emission, 43Sigma+ → 1(a)3Sigma +, was used to determine both the absolute vibrational numbering and the transition dipole moment function M(R). Each (upsilon, N) level is typically split into three sets of sublevels by the Fermi contact interaction bFI·S. Further splitting (of order 0.004 cm-1) has been attributed to the spin-rotation interaction gammaN·S. The values of bF that fit the data best are ˜(0.99 +/- 0.04) x 10-2 cm-1, with weak dependence on upsilon. The best fit values of gamma are in the range 1--6 x 10-4 cm-1 and depend strongly on upsilon.

The fine-structure intervals of (N-14)+ by far-infrared laser magnetic resonance

NASA Technical Reports Server (NTRS)

Brown, John M.; Varberg, Thomas D.; Evenson, Kenneth M.; Cooksy, Andrew L.

1994-01-01

The far-infrared laser magnetic resonance spectra associated with both fine-structure transitions in (N-14)+ in its ground P-3 state have been recorded. This is the first laboratory observation of the J = 1 left arrow 0 transition and its frequency has been determined two orders of magnitude more accurately than previously. The remeasurement of the J = 2 left arrow 1 spectrum revealed a small error in the previous laboratory measurements. The fine-structure splittings (free of hyperfine interactions) determined in this work are (delta)E(sub 10) = 1461.13190 (61) GHz, (delta)E(sub 21) = 2459.38006 (37) GHz. Zero-field transition frequencies which include the effects of hyperfine structure have also been calculated. Refined values for the hyperfine constants and the g(sub J) factors have been obtained.

Electron paramagnetic resonance and density-functional theory studies of Cu(II)-bis(oxamato) complexes.

PubMed

Bräuer, Björn; Weigend, Florian; Fittipaldi, Maria; Gatteschi, Dante; Reijerse, Edward J; Guerri, Annalisa; Ciattini, Samuele; Salvan, Georgeta; Rüffer, Tobias

2008-08-04

In this work we present the investigation of the influence of electronic and structural variations induced by varying the N,N'-bridge on the magnetic properties of Cu(II)- bis(oxamato) complexes. For this study the complexes [Cu(opba)] (2-) ( 1, opba = o-phenylene- bis(oxamato)), [Cu(nabo)] (2-) ( 2, nabo = 2,3-naphthalene- bis(oxamato)), [Cu(acbo)] (2-) ( 3, acbo = 2,3-anthrachinone- bis(oxamato)), [Cu(pba)] (2-) ( 4, pba = propylene- bis(oxamato)), [Cu(obbo)] (2-) ( 5, obbo = o-benzyl- bis(oxamato)), and [Cu(npbo)] (2-) ( 6, npbo = 1,8-naphthalene- bis(oxamato)), and the respective structurally isomorphic Ni(II) complexes ( 8- 13) have been prepared as ( (n)Bu 4N) (+) salts. The new complex ( (n)Bu 4N) 2[Cu(R-bnbo)].2H 2O ( 7, R-bnbo = (R)-1,1'-binaphthalene-2,2'- bis(oxamato)) was synthesized and is the first chiral complex in the series of Cu(II)-bis(oxamato) complexes. The molecular structure of 7 has been determined by single crystal X-ray analysis. The Cu(II) ions of the complexes 1- 7 are eta (4)(kappa (2) N, kappa (2) O) coordinated with a more or less distorted square planar geometry for 1- 6 and a distorted tetrahedral geometry for 7. Using pulsed Electron Nuclear Double Resonance on complex 6, detailed information about the relative orientation of the hyperfine ( A) and nuclear quadrupole tensors ( Q) of the coordinating nitrogens with respect to the g tensor were obtained. Electron Paramagnetic Resonance studies in the X, Q, and W-band at variable temperatures were carried out to extract g and A values of N ligands and Cu ion for 1- 7. The hyperfine values were interpreted in terms of spin population on the corresponding atoms. The obtained trends of the spin population for the monomeric building blocks were shown to correlate to the trends obtained in the dependence of the exchange interaction of the corresponding trinuclear complexes on their geometry.

Two-photon exchange correction to the hyperfine splitting in muonic hydrogen

NASA Astrophysics Data System (ADS)

Tomalak, Oleksandr

2017-12-01

We reevaluate the Zemach, recoil and polarizability corrections to the hyperfine splitting in muonic hydrogen expressing them through the low-energy proton structure constants and obtain the precise values of the Zemach radius and two-photon exchange (TPE) contribution. The uncertainty of TPE correction to S energy levels in muonic hydrogen of 105 ppm exceeds the ppm accuracy level of the forthcoming 1S hyperfine splitting measurements at PSI, J-PARC and RIKEN-RAL.

Conventional electron paramagnetic resonance of Mn2+ in synthetic hydroxyapatite at different concentrations of the doped manganese

NASA Astrophysics Data System (ADS)

Murzakhanov, F.; Mamin, G.; Voloshin, A.; Klimashina, E.; Putlyaev, V.; Doronin, V.; Bakhteev, S.; Yusupov, R.; Gafurov, M.; Orlinskii, S.

2018-05-01

Powders of synthetic hydroxyapatite doped with Mn2+ ions in concentrations from 0.05 till 5 wt. % were investigated by conventional electron paramagnetic resonance (EPR). The parameters of the spin-Hamiltonian are derived. Partially resolved hyperfine structure in the magnetic fields corresponding to g ≈ 4.3 and g ≈ 9.4 is observed. The narrowing of the central peak with concentration is reported. A possibility to use the linewidth and intensity of the central peak for concentration measurements are discussed. The results could be used for the identification and qualification of Mn2+ in oil, mining and ore formations.

Oxygen-17 and molybdenum-95 coupling in spectroscopic models of molybdoenzymes

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

Wilson, G.L.; Kony, M.; Tiekink, E.R.

1988-09-28

Assignment of (Mo/sup V/OS) and cis-(Mo/sup V/O(SH)) centers in active xanthine oxidase (very rapid and rapid ESR signals) are supported by generation of these species in solution. The ESR parameters were measured using /sup 17/O and /sup 95/Mo and are reported herein. The data revealed variations in relative magnitudes of the hyperfine components, and the different patterns of angles reflect significant differences in electronic structure. The same electronic differences appear to be responsible for the variations in magnitude and anisotropy of the /sup 17/O coupling, assigned to bound product Mo-/sup 17/OR in both enzyme signals.

Sensitive sub-Doppler nonlinear spectroscopy for hyperfine-structure analysis using simple atomizers

NASA Astrophysics Data System (ADS)

Mickadeit, Fritz K.; Kemp, Helen; Schafer, Julia; Tong, William M.

1998-05-01

Laser wave-mixing spectroscopy is presented as a sub-Doppler method that offers not only high spectral resolution, but also excellent detection sensitivity. It offers spectral resolution suitable for hyperfine structure analysis and isotope ratio measurements. In a non-planar backward- scattering four-wave mixing optical configuration, two of the three input beams counter propagate and the Doppler broadening is minimized, and hence, spectral resolution is enhanced. Since the signal is a coherent beam, optical collection is efficient and signal detection is convenient. This simple multi-photon nonlinear laser method offers un usually sensitive detection limits that are suitable for trace-concentration isotope analysis using a few different types of simple analytical atomizers. Reliable measurement of hyperfine structures allows effective determination of isotope ratios for chemical analysis.

Hyperfine excitation of linear molecules by para- and ortho-H{sub 2}: Application to the HCl–H{sub 2} system

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

Lanza, Mathieu; Lique, François, E-mail: francois.lique@univ-lehavre.fr

The determination of hyperfine structure resolved excitation cross sections and rate coefficients due to H{sub 2} collisions is required to interpret astronomical spectra. In this paper, we present several theoretical approaches to compute these data. An almost exact recoupling approach and approximate sudden methods are presented. We apply these different approaches to the HCl–H{sub 2} collisional system in order to evaluate their respective accuracy. HCl–H{sub 2} hyperfine structure resolved cross sections and rate coefficients are then computed using recoupling and approximate sudden methods. As expected, the approximate sudden approaches are more accurate when the collision energy increases and the resultsmore » suggest that these approaches work better for para-H{sub 2} than for ortho-H{sub 2} colliding partner. For the first time, we present HCl–H{sub 2} hyperfine structure resolved rate coefficients, computed here for temperatures ranging from 5 to 300 K. The usual Δj{sub 1} = ΔF{sub 1} propensity rules are observed for the hyperfine transitions. The new rate coefficients will significantly help the interpretation of interstellar HCl emission lines observed with current and future telescopes. We expect that these new data will allow a better determination of the HCl abundance in the interstellar medium, that is crucial to understand the interstellar chlorine chemistry.« less

Electron paramagnetic resonance study of neutral Mg acceptors in β-Ga2O3 crystals

NASA Astrophysics Data System (ADS)

Kananen, B. E.; Halliburton, L. E.; Scherrer, E. M.; Stevens, K. T.; Foundos, G. K.; Chang, K. B.; Giles, N. C.

2017-08-01

Electron paramagnetic resonance (EPR) is used to directly observe and characterize neutral Mg acceptors ( M gGa0 ) in a β-Ga2O3 crystal. These acceptors, best considered as small polarons, are produced when the Mg-doped crystal is irradiated at or near 77 K with x rays. During the irradiation, neutral acceptors are formed when holes are trapped at singly ionized Mg acceptors ( M gGa- ). Unintentionally present Fe3+ (3d5) and Cr3+ (3d3) transition-metal ions serve as the corresponding electron traps. The hole is localized in a nonbonding p orbital on a threefold-coordinated oxygen ion adjacent to an Mg ion at a sixfold-coordinated Ga site. These M gGa0 acceptors (S = 1/2) have a slightly anisotropic g matrix (principal values are 2.0038, 2.0153, and 2.0371). There is also partially resolved 69Ga and 71Ga hyperfine structure resulting from unequal interactions with the two Ga ions adjacent to the hole. With the magnetic field along the a direction, hyperfine parameters are 2.61 and 1.18 mT for the 69Ga nuclei at the two inequivalent neighboring Ga sites. The M gGa0 acceptors thermally convert back to their nonparamagnetic M gGa- charge state when the temperature of the crystal is raised above approximately 250 K.

Nuclear Hyperfine Structure in the Donor – Acceptor Complexes (CH3)3N-BF3 and (CH)33N-B(CH3)3

EPA Science Inventory

The donor-acceptor complexes (CH3)3N-BF3 and (CH3)3N-B(CH3)3 have been reinvestigated at high resolution by rotational spectroscopy in a supersonic jet. Nuclear hyperfine structure resulting from both nitrogen and boron has been resolved and quadrupole coupling constants have bee...

The pure rotational spectrum of TiF (X 4Φr): 3d transition metal fluorides revisited

NASA Astrophysics Data System (ADS)

Sheridan, P. M.; McLamarrah, S. K.; Ziurys, L. M.

2003-11-01

The pure rotational spectrum of TiF in its X 4Φr (v=0) ground state has been measured using millimeter/sub-millimeter wave direct absorption techniques in the range 140-530 GHz. In ten out of the twelve rotational transitions recorded, all four spin-orbit components were observed, confirming the 4Φr ground state assignment. Additional small splittings were resolved in several of the spin components in lower J transitions, which appear to arise from magnetic hyperfine interactions of the 19F nucleus. In contrast, no evidence for Λ-doubling was seen in the data. The rotational transitions of TiF were analyzed using a case (a) Hamiltonian, resulting in the determination of rotational and fine structure constants, as well as hyperfine parameters for the fluorine nucleus. The data were readily fit in a case (a) basis, indicating strong first order spin-orbit coupling and minimal second-order effects, as also evidenced by the small value of λ, the spin-spin parameter. Moreover, only one higher order term, η, the spin-orbit/spin-spin interaction term, was needed in the analysis, again suggesting limited perturbations in the ground state. The relative values of the a, b, and c hyperfine constants indicate that the three unpaired electrons in this radical lie in orbitals primarily located on the titanium atom and support the molecular orbital picture of TiF with a σ1δ1π1 single electron configuration. The bond length of TiF (1.8342 Å) is significantly longer than that of TiO, suggesting that there are differences in the bonding between 3d transition metal fluorides and oxides.

Experimental observation and determination of the laser-induced frequency shift of hyperfine levels of ultracold polar molecules

NASA Astrophysics Data System (ADS)

Liu, Wenliang; Wang, Xiaofeng; Wu, Jizhou; Su, Xingliang; Wang, Shen; Sovkov, Vladimir B.; Ma, Jie; Xiao, Liantuan; Jia, Suotang

2017-08-01

We report on the experimental observation and quantitative determination of the laser-induced frequency shift (LIFS) of the ultracold polar molecules formed by photoassociation (PA). The experiments are performed by detecting a series of double PA spectra with a molecular hyperfine structure, which are induced by two PA lasers with a precise and adjustable frequency reference. We find that the LIFS of the molecular hyperfine levels shows a linear dependence on PA laser intensity.

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.

Redox-dependent structure change and hyperfine nuclear magnetic resonance shifts in cytochrome c

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

Feng, Yiquing; Roder, H.; Englander, S.W.

1990-04-10

Proton nuclear magnetic resonance assignments for reduced and oxidized equine cytochrome c show that many individual protons exhibit different chemical shifts in the two protein forms, reflecting diamagnetic shift effects due to structure change, and in addition contact and pseudocontact shifts that occur only in the paramagnetic oxidized form. To evaluate the chemical shift differences for structure change, the authors removed the pseudocontact shift contribution by a calculation based on knowledge of the electron spin g tensor. The g-tensor calculation, when repeated using only 12 available C{sub {alpha}}H proton resonances for cytochrom c from tuna, proved to be remarkably stable.more » The derived g tensor was then used together with spatial coordinates for the oxidized form to calculate the pseudocontact shift contribution to proton resonances at 400 identifiable sites throughout the protein, so that the redox-dependent chemical shift discrepancy, could be evaluated. Large residual changes in chemical shift define the Fermi contact shifts, where are found as expected to be limited to the immediate covalent structure of the heme and its ligands and to be asymmetrically distributed over the heme. The chemical shift discrepancies observed appear in the main to reflect structure-dependent diamagnetic shifts rather than hyperfine effects due to displacements in the pseudocontact shift field. Although 51 protons in 29 different residues exhibit significant chemical shift changes, the general impressions one of small structural adjustments to redox-dependent strain rather than sizeable structural displacements or rearrangements.« less

Hyperfine-resolved 3.4-{mu}m spectroscopy of CH{sub 3}I with a widely tunable difference frequency generation source and a cavity-enhanced cell: A case study of a local Coriolis interaction between the v{sub 1}=1 and (v{sub 2},v{sub 6}{sup l})=(1,2{sup 2}) states

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

Okubo, Sho; Nakayama, Hirotaka; Sasada, Hiroyuki

Saturated absorption spectra of the {nu}{sub 1} fundamental band of CH{sub 3}I are recorded with a cavity-enhanced cell and a tunable difference frequency generation source having an 86-cm{sup -1} range. The recorded spectral lines are 250 kHz wide, and most of them are resolved into the individual hyperfine components. The Coriolis interaction between the v{sub 1}=1 and (v{sub 2},v{sub 6}{sup l})=(1,2{sup 2}) states locally perturbing the hyperfine structures is analyzed to yield the Coriolis and hyperfine coupling constants with uncertainties similar to those in typical microwave spectroscopy. The spectrometer has demonstrated the potential for precisely determining the energy structure inmore » the vibrational excited states.« less

Hyperfine structure and isotope shift analysis of singly ionized titanium

NASA Astrophysics Data System (ADS)

Bouazza, Safa

2013-04-01

The even-parity low configuration system of Ti II has been considered on the basis of the experimental data found in the literature, and its fine structure has been reanalyzed by simultaneous parameterization of one- and two-body interactions for the model space (3d + 4s)3. Furthermore, the main one-electron hyperfine structure parameters for these configurations have been evaluated. For instance, for 3d24s1, a_{3{\\rm{d}}}^{01} = - {\\rm{63}}.{\\rm{2}}\\left( {{\\rm{3}}.{\\rm{1}}} \\right)\\,{\\rm{MHz}} and a_{4{\\rm{s}}}^{10} = - {\\rm{984}}.{\\rm{1}}\\left( {{\\rm{7}}.{\\rm{1}}} \\right)\\,{\\rm{MHz}} . Field shifts (FS) and specific mass shifts (SMS) of the main Ti II configurations are deduced by means of ab initio estimates combined with a small quantity of experimental isotope shift data available in the literature: FS(3d3) = -63.3 MHz, FS(3d24p1) = -49.7 MHz, FS(3d14s2) = 98.2 MHz, FS(4s24P1) = 163.4 MHz and SMS(3d3) = 1453.3 MHz, SMS(3d14s2) = -2179.7 MHz, …, referred to 3d24s1 for the pair Ti46-Ti48.

Opto-Electronic Oscillator Stabilized By A Hyperfine Atomic Transition

NASA Technical Reports Server (NTRS)

Strekalov, Dmitry; Aveline, David; Matsko, Andrey B.; Thompson, Robert; Yu, Nan

2004-01-01

Opto-electronic oscillator (OEO) is a closed-loop system with part of the loop is implemented by an optical beam, and the rest by RF circuitry. The technological advantage of this approach over traditional all-RF loops in the gigahertz range comes from the that frequency filtering can be done far more efficiently in the optical range with compact, low power, and have superior stability. In this work, we report our preliminary results on using the phenomenon of coherent population trapping in (87) Rb vapor as an optical filter. Such a filter allows us to stabilize the OEO at the hyperfine splitting frequency of rubidium, thus implementing a novel type of frequency standard.

Properties of Gd{sub 2}O{sub 3} nanoparticles studied by hyperfine interactions and magnetization measurements

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

Correa, E. L., E-mail: eduardo.correa@usp.br; Bosch-Santos, B.; Cavalcante, F. H. M.

2016-05-15

The magnetic behavior of Gd{sub 2}O{sub 3} nanoparticles, produced by thermal decomposition method and subsequently annealed at different temperatures, was investigated by magnetization measurements and, at an atomic level, by perturbed γ − γ angular correlation (PAC) spectroscopy measuring hyperfine interactions at {sup 111}In({sup 111}Cd) probe nuclei. Nanoparticle structure, size and shape were characterized by X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM). Magnetization measurements were carried out to characterize the paramagnetic behavior of the samples. XRD results show that all samples crystallize in the cubic-C form of the bixbyite structure with space group Ia3. TEM images showed that particlesmore » annealed at 873 K present particles with highly homogeneous sizes in the range from 5 nm to 10 nm and those annealed at 1273 K show particles with quite different sizes from 5 nm to 100 nm, with a wide size distribution. PAC and magnetization results show that samples annealed at 873 and 1273 K are paramagnetic. Magnetization measurements show no indication of blocking temperatures for all samples down to 2 K and the presence of antiferromagnetic correlations.« less

EPR and FTIR spectroscopic studies of MO-Al2O3-Bi2O3-B2O3-MnO2(M = Pb, Zn and Cd) glasses

NASA Astrophysics Data System (ADS)

Lalitha Phani, A. V.; Sekhar, K. Chandra; Chakradhar, R. P. S.; Narasimha Chary, M.; Shareefuddin, Md

2018-03-01

Glasses of the system (30-x)MO-xAl2O3-15Bi2O3-54.5B2O3-0.5MnO2 [M = Pb, Zn & Cd] (x = 0, 5, 10 & 15 mol%) were prepared by the normal melt quenching method. The amorphous nature of the prepared glasses was confirmed by the XRD studies. The EPR and FTIR studies were carried out at room temperature (RT). The EPR spectra exhibited three resonance signals at g ≈ 2.0 with a hyperfine structure, an absorption around g = 4.3 and a distinct shoulder at g = 3.3. Deconvoluted spectra were drawn for g ≈ 2.0 to resolve the six hyperfine lines. The electron paramagnetic resonance signal at g ≈ 2.0 indicates that the Mn2+ ions are in nearly perfectly octahedral symmetry. The low field signals at g = 3.3 and g = 4.3 are attributed to the Mn2+ ion which are in distorted rhombic symmetries. The hyperfine (HF) splitting constant (A) values suggested that the bonding between Mn2+ ions and its ligands is ionic in nature. The presence of BO3 and BO4 borate units, metal oxide cation units, Mn2+ and Bi-O bond vibrations in BiO3 units were noticed from the FTIR spectra.

Optogalvanic spectroscopy of lanthanum hyperfine structure

NASA Astrophysics Data System (ADS)

Nelson, Amanda; Hankes, Jessie; Banner, Patrick; Olmschenk, Steven

2017-04-01

Optogalvanic spectroscopy is a sensitive technique to measure optical transitions of atoms and ions produced in a high voltage discharge. Advantages of this technique include a comparatively simple optical setup and the ability to interrogate excited state transitions. Here, we use optogalavanic spectroscopy in a hollow cathode lamp to measure the hyperfine spectrum of several transitions in lanthanum. Hyperfine coefficients are determined for the corresponding energy levels and compared to available previous measurements. This research is supported by the Army Research Office, Research Corporation for Science Advancement, and Denison University.

Fine- and hyperfine structure investigations of even configuration system of atomic terbium

NASA Astrophysics Data System (ADS)

Stefanska, D.; Elantkowska, M.; Ruczkowski, J.; Furmann, B.

2017-03-01

In this work a parametric study of the fine structure (fs) and the hyperfine structure (hfs) for the even-parity configurations of atomic terbium (Tb I) is presented, based in considerable part on the new experimental results. Measurements on 134 spectral lines were performed by laser induced fluorescence (LIF) in a hollow cathode discharge lamp; on this basis, the hyperfine structure constants A and B were determined for 52 even-parity levels belonging to the configurations 4f85d6s2, 4f85d26s or 4f96s6p; in all the cases those levels were involved in the transitions investigated as the lower levels. For 40 levels the hfs was examined for the first time, and for the remaining 12 levels the new measurements supplement our earlier results. As a by-product, also preliminary values of the hfs constants for 84 odd-parity levels were determined (the investigations of the odd-parity levels system in the terbium atom are still in progress). This huge amount of new experimental data, supplemented by our earlier published results, were considered for the fine and hyperfine structure analysis. A multi-configuration fit of 7 configurations was performed, taking into account second-order of perturbation theory, including the effects of closed shell-open shell excitations. Predicted values of the level energies, as well as of magnetic dipole and electric quadrupole hyperfine structure constants A and B, are quoted in cases when no experimental values are available. By combining our experimental data with our own semi-empirical procedure it was possible to identify correctly the lower and upper level of the line 544.1440 nm measured by Childs with the use of the atomic-beam laser-rf double-resonance technique (Childs, J Opt Soc Am B 9;1992:191-6).

Observation of photoassociation of ultracold sodium and cesium at the asymptote Na (3S1/2) + Cs (6P1/2)

NASA Astrophysics Data System (ADS)

Wu, Jizhou; Liu, Wenliang; Wang, Xiaofeng; Ma, Jie; Li, Dan; Sovkov, Vladimir B.; Xiao, Liantuan; Jia, Suotang

2018-05-01

We report on the production of ultracold heteronuclear NaCs* molecules in a dual-species magneto-optical trap through photoassociation. The electronically excited molecules are formed below the Na (3S1/2) + Cs (6P1/2) dissociation limit. 12 resonance lines are detected using trap-loss spectroscopy based on a highly sensitive modulation technique. The highest observed rovibrational level exhibits clear hyperfine structure, which is detected for the first time. This structure is simulated within a simplified model consisting of 4 coupled levels belonging to the initially unperturbed Hund's case "a" electronic states, which have been explored in our previous work that dealt with the Na (3S1/2) + Cs (6P3/2) asymptote [W. Liu et al., Phys. Rev. A 94, 032518 (2016)].

Zero Quantum Coherence in a Series of Covalent Spin-Correlated Radical Pairs.

PubMed

Nelson, Jordan N; Krzyaniak, Matthew D; Horwitz, Noah E; Rugg, Brandon K; Phelan, Brian T; Wasielewski, Michael R

2017-03-23

Photoinitiated subnanosecond electron transfer within covalently linked electron donor-acceptor molecules can result in the formation of a spin-correlated radical pair (SCRP) with a well-defined initial singlet spin configuration. Subsequent coherent mixing between the SCRP singlet and triplet m s = 0 spin states, the so-called zero quantum coherence (ZQC), is of potential interest in quantum information processing applications because the ZQC can be probed using pulse electron paramagnetic resonance (pulse-EPR) techniques. Here, pulse-EPR spectroscopy is utilized to examine the ZQC oscillation frequencies and ZQC dephasing in three structurally well-defined D-A systems. While transitions between the singlet and triplet m s = 0 spin states are formally forbidden (Δm s = 0), they can be addressed using specific microwave pulse turning angles to map information from the ZQC onto observable single quantum coherences. In addition, by using structural variations to tune the singlet-triplet energy gap, the ZQC frequencies determined for this series of molecules indicate a stronger dependence on the electronic g-factor than on electron-nuclear hyperfine interactions.

Hyperfine coupling of the iodine {\\boldsymbol{D}}{0}_{{\\boldsymbol{u}}}^{+} and β1 g ion-pair states

NASA Astrophysics Data System (ADS)

Baturo, V. V.; Cherepanov, I. N.; Lukashov, S. S.; Petrov, A. N.; Poretsky, S. A.; Pravilov, A. M.

2018-05-01

Detailed studies of I2(β1 g , v β = 13, J β ∼ D{0}u+, v D = 12, J D and D, 48, J D ∼ β, 47, J β ) rovibronic state coupling have been carried out using two-step two-color, hν 1 + hν 2 and hν 1 + 2hν 2, optical–optical double resonance excitation schemes, respectively. The hyperfine interaction satisfying the | {{Δ }}J| = 0, 1 selection rules (magnetic-dipole interaction) has been observed. No electric-quadrupole hyperfine coupling (| {{Δ }}J| = 2) has been found. The dependences of ratios of luminescence intensities from the rovibronic states populated due to the hyperfine coupling to those from optically populated ones on energy gaps between these states have been experimentally determined. The matrix elements as well as the hyperfine structure constant have been obtained using these dependences. It is shown that they increase slightly with the vibrational quantum number of the states.

VizieR Online Data Catalog: Rotational frequencies of TiO isotopologues (Lincowski+, 2016)

NASA Astrophysics Data System (ADS)

Lincowski, A. P.; Halfen, D. T.; Ziurys, L. M.

2017-03-01

Pure rotational spectra of the rare isotopologues of titanium oxide, 46TiO, 47TiO, 49TiO, and 50TiO, have been recorded using a combination of Fourier transform millimeter-wave (FTmmW) and millimeter/submillimeter direct absorption techniques in the frequency range 62-538GHz. This study is the first complete spectroscopic characterization of these species in their X3Δr ground electronic states. The isotopologues were created by the reaction of N2O or O2 and titanium vapor, produced either by laser ablation or in a Broida-type oven, and observed in the natural Ti isotopic abundances. Between 10 and 11 rotational transitions J+1<->J were measured for each species, typically in all 3 spin-orbit ladders Ω=1, 2, and 3. For 47TiO and 49TiO, hyperfine structure was resolved, originating from the titanium-47 and titanium-49 nuclear spins of I=5/2 and 7/2, respectively. For the Ω=1 and 3 components, the hyperfine structure was found to follow a classic Lande pattern, while that for Ω=2 appeared to be perturbed, likely a result of mixing with the nearby isoconfigurational a1Δ state. The spectra were analyzed with a case (a) Hamiltonian, and rotational, spin-orbit, and spin-spin parameters were determined for each species, as well as magnetic hyperfine and electric quadrupole constants for the two molecules with nuclear spins. The most abundant species, 48TiO, has been detected in circumstellar envelopes. These measurements will enable other titanium isotopologues to be studied at millimeter wavelengths, providing Ti isotope ratios that can test models of nucleosynthesis. (1 data file).

Millimeter/Submillimeter Spectroscopy of TiO (X3Δr): The Rare Titanium Isotopologues

NASA Astrophysics Data System (ADS)

Lincowski, A. P.; Halfen, D. T.; Ziurys, L. M.

2016-12-01

Pure rotational spectra of the rare isotopologues of titanium oxide, 46TiO, 47TiO, 49TiO, and 50TiO, have been recorded using a combination of Fourier transform millimeter-wave (FTmmW) and millimeter/submillimeter direct absorption techniques in the frequency range 62-538 GHz. This study is the first complete spectroscopic characterization of these species in their X 3Δ r ground electronic states. The isotopologues were created by the reaction of N2O or O2 and titanium vapor, produced either by laser ablation or in a Broida-type oven, and observed in the natural Ti isotopic abundances. Between 10 and 11 rotational transitions J + 1 ≤ftrightarrow J were measured for each species, typically in all 3 spin-orbit ladders Ω = 1, 2, and 3. For 47TiO and 49TiO, hyperfine structure was resolved, originating from the titanium-47 and titanium-49 nuclear spins of I = 5/2 and 7/2, respectively. For the Ω = 1 and 3 components, the hyperfine structure was found to follow a classic Landé pattern, while that for Ω = 2 appeared to be perturbed, likely a result of mixing with the nearby isoconfigurational a 1Δ state. The spectra were analyzed with a case (a) Hamiltonian, and rotational, spin-orbit, and spin-spin parameters were determined for each species, as well as magnetic hyperfine and electric quadrupole constants for the two molecules with nuclear spins. The most abundant species, 48TiO, has been detected in circumstellar envelopes. These measurements will enable other titanium isotopologues to be studied at millimeter wavelengths, providing Ti isotope ratios that can test models of nucleosynthesis.

What the multiline signal (MLS) simulation data with average of weighted computations reveal about the Mn hyperfine interactions and oxidation states of the manganese cluster in OEC?

NASA Astrophysics Data System (ADS)

Baituti, Bernard

2017-11-01

Understanding the structure of oxygen evolving complex (OEC) fully still remains a challenge. Lately computational chemistry with the data from more detailed X-ray diffraction (XRD) OEC structure, has been used extensively in exploring the mechanisms of water oxidation in the OEC (Gatt et al., J. Photochem. Photobiol. B 104(1-2), 80-93 2011). Knowledge of the oxidation states is very crucial for understanding the core principles of catalysis by photosystem II (PSII) and catalytic mechanism of OEC. The present study involves simulation studies of the X-band continuous wave electron-magnetic resonance (CW-EPR) generated S 2 state signals, to investigate whether the data is in agreement with the four manganese ions in the OEC, being organised as a `3 + 1' (trimer plus one) model (Gatt et al., Angew. Chem. Int. Ed. 51, 12025-12028 2012; Petrie et al., Chem. A Eur. J. 21, 6780-6792 2015; Terrett et al., Chem. Commun. (Camb.) 50, 8-11 2014) or `dimer of dimers' model (Terrett et al. 2016). The question that still remains is how much does each Mn ion contribute to the " g2multiline" signal through its hyperfine interactions in OEC also to differentiate between the `high oxidation state (HOS)' and `low oxidation state (LOS)' paradigms? This is revealed in part by the structure of multiline (ML) signal studied in this project. Two possibilities have been proposed for the redox levels of the Mn ions within the catalytic cluster, the so called `HOS' and `LOS' paradigms (Gatt et al., J. Photochem. Photobiol. B 104(1-2), 80-93 2011). The method of data analysis involves numerical simulations of the experimental spectra on relevant models of the OEC cluster. The simulations of the X-band CW-EPR multiline spectra, revealed three manganese ions having hyperfine couplings with large anisotropy. These are most likely Mn III centres and these clearly support the `LOS' OEC paradigm model, with a mean oxidation of 3.25 in the S2 state. This is consistent with the earlier data by Jin et al. (Phys. Chem. Chem. Phys. (PCCP) 16(17), 7799-812 2014), but the present results clearly indicate that heterogeneity in hyperfine couplings exist in samples as typically prepared.

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.

Ab initio theory of point defects in oxide materials: structure, properties, chemical reactivity

NASA Astrophysics Data System (ADS)

Pacchioni, Gianfranco

2000-05-01

Point defects play a fundamental role in determining the physical and chemical properties of inorganic materials. This holds not only for the bulk properties but also for the surface of oxides where several kinds of point defects exist and exhibit a rich and complex chemistry. A particularly important defect in oxides is the oxygen vacancy. Depending on the electronic structure of the material the nature of oxygen vacancies changes dramatically. In this article we provide a rationalization of the very different electronic structure of neutral and charged oxygen vacancies in SiO 2 and MgO, two oxide materials with completely different electronic structure (from very ionic, MgO, to largely covalent, SiO 2). We used methods of ab initio quantum chemistry, from density functional theory (DFT) to configuration interaction (CI), to determine the ground and excited state properties of these defects. The theoretical results are combined with recent spectroscopic measurements. A series of observable properties has been determined in this way: defect formation energies, hyperfine interactions in electron paramagnetic resonance (EPR) spectra of paramagnetic centers, optical spectra, surface chemical reactivity. The interplay between experimental and theoretical information allows one to unambiguously identify the structure of oxygen vacancies in these binary oxides and on their surfaces.

The hyperfine structure in the rotational spectra of D{sub 2}{sup 17}O and HD{sup 17}O: Confirmation of the absolute nuclear magnetic shielding scale for oxygen

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

Puzzarini, Cristina, E-mail: cristina.puzzarini@unibo.it; Cazzoli, Gabriele; Harding, Michael E.

2015-03-28

Guided by theoretical predictions, the hyperfine structures of the rotational spectra of mono- and bideuterated-water containing {sup 17}O have been experimentally investigated. To reach sub-Doppler resolution, required to resolve the hyperfine structure due to deuterium quadrupole coupling as well as to spin-rotation (SR) and dipolar spin-spin couplings, the Lamb-dip technique has been employed. The experimental investigation and in particular, the spectral analysis have been supported by high-level quantum-chemical computations employing coupled-cluster techniques and, for the first time, a complete experimental determination of the hyperfine parameters involved was possible. The experimentally determined {sup 17}O spin-rotation constants of D{sub 2}{sup 17}O andmore » HD{sup 17}O were used to derive the paramagnetic part of the corresponding nuclear magnetic shielding constants. Together with the computed diamagnetic contributions as well as the vibrational and temperature corrections, the latter constants have been employed to confirm the oxygen nuclear magnetic shielding scale, recently established on the basis of spin-rotation data for H{sub 2}{sup 17}O [Puzzarini et al., J. Chem. Phys. 131, 234304 (2009)].« less

The NaK 1 1,3delta states: theoretical and experimental studies of fine and hyperfine structure of rovibrational levels near the dissociation limit.

PubMed

Wilkins, A D; Morgus, L; Hernandez-Guzman, J; Huennekens, J; Hickman, A P

2005-09-22

Earlier high-resolution spectroscopic studies of the fine and hyperfine structure of rovibrational levels of the 1 3delta state of NaK have been extended to include high lying rovibrational levels with v < or = 59, of which the highest levels lie within approximately 4 cm(-1) of the dissociation limit. A potential curve is determined using the inverted perturbation approximation method that reproduces these levels to an accuracy of approximately 0.026 cm(-1). For the largest values of v, the outer turning points occur near R approximately 12.7 angstroms, which is sufficiently large to permit the estimation of the C6 coefficient for this state. The fine and hyperfine structure of the 1 3delta rovibrational levels has been fit using the matrix diagonalization method that has been applied to other states of NaK, leading to values of the spin-orbit coupling constant A(v) and the Fermi contact constant b(F). New values determined for v < or = 33 are consistent with values determined by a simpler method and reported earlier. The measured fine and hyperfine structure for v in the range 44 < or = v < or = 49 exhibits anomalous behavior whose origin is believed to be the mixing between the 1 3delta and 1 1delta states. The matrix diagonalization method has been extended to treat this interaction, and the results provide an accurate representation of the complicated patterns that arise. The analysis leads to accurate values for A(v) and b(F) for all values of v < or = 49. For higher v (50 < or = v < or = 59), several rovibrational levels have been assigned, but the pattern of fine and hyperfine structure is difficult to interpret. Some of the observed features may arise from effects not included in the current model.

(Charge separation in photoredox reactions). Informal annual technical progress report, October 1, 1981-October 1, 1982. [N,N,N',N'tetramethylbenzidine

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

Kevan, L.

1982-10-21

During this period work has focused on the structural aspects of photoinduced charge separation in micellar media with initial forays into vesicular media. The primary techniques utilized are electron spin resonance and electron spin echo spectrometry. The analysis of electron spin echo modulation gives a unique handle on very weak hyperfine interactions thus providing a new structural tool for this general problem. Electron spin resonance and electron spin echo studies of the photoionization of N,N,N',N'tetramethylbenzidine (TMB) to give the cation radical have been carried out in anionic, cationic and nonionic micellar solutions frozen to 77/sup 0/K. The photoionization efficiency ofmore » TMB has also been studied in micelles with varying alkyl chain lengths of the surfactant. Stearic acid nitroxide spin probes have also been used to determine some structural aspects of the location of the neutral TMB molecule in anionic micelles before photoionization. The nitroxide work in which the nitroxide is acting as an electron acceptor also shows that a suitable electron acceptor can be located within the micellar structure. The effect of inorganic solutes on the efficiency of the photoionization of TMB in frozen micelles has also been studied. A series of electron scavenger studies have been initiated to study the effect on TMB photoionization efficiency. Electron spin echo detection of laser photogenerated TMB cation in liquid sodium dodecyl sulfate solutions at room temperature has recently been observed.« less

Ultrafast Study of Dynamic Exchange Coupling in Ferromagnet/Oxide/Semiconductor Heterostructures

NASA Astrophysics Data System (ADS)

Ou, Yu-Sheng

Spintronics is the area of research that aims at utilizing the quantum mechanical spin degree of freedom of electrons in solid-state materials for information processing and data storage application. Since the discovery of the giant magnetoresistance, the field of spintronics has attracted lots of attention for its numerous potential advantages over contemporary electronics, such as less power consumption, high integration density and non-volatility. The realization of a spin battery, defined by the ability to create spin current without associated charge current, has been a long-standing goal in the field of spintronics. The demonstration of pure spin current in ferromagnet/nonmagnetic material hybrid structures by ferromagnetic resonance spin pumping has defined a thrilling direction for this field. As such, this dissertation targets at exploring the spin and magnetization dynamics in ferromagnet/oxide/semiconductor heterostructures (Fe/MgO/GaAs) using time-resolved optical pump-probe spectroscopy with the long-range goal of understanding the fundamentals of FMR-driven spin pumping. Fe/GaAs heterostructures are complex systems that contain multiple spin species, including paramagnetic spins (GaAs electrons), nuclear spins (Ga and As nuclei) and ferromagnetic spins (Fe). Optical pump-probe studies on their interplay have revealed a number of novel phenomena that has not been explored before. As such they will be the major focus of this dissertation. First, I will discuss the effect of interfacial exchange coupling on the GaAs free-carrier spin relaxation. Temperature- and field-dependent spin-resolved pump-probe studies reveal a strong correlation of the electron spin relaxation with carrier freeze-out, in quantitative agreement with a theoretical interpretation that at low temperatures the free-carrier spin lifetime is dominated by inhomogeneity in the local hyperfine field due to carrier localization. Second, we investigate the impact of tunnel barrier thickness on GaAs electron spin dynamics in Fe/MgO/GaAs heterostructures. Comparison of the Larmor frequency between samples with thick and thin MgO barriers reveals a four-fold variation in exchange coupling strength, and investigation of the spin lifetimes argues that inhomogeneity in the local hyperfine field dominates free-carrier spin relaxation across the entire range of barrier thickness. These results provide additional evidence to support the theory of hyperfine-dominated spin relaxation in GaAs. Third, we investigated the origin and dynamics of an emergent spin population by pump power and magnetic field dependent spin-resolved pump-probe studies. Power dependent study confirms its origin to be filling of electronic states in GaAs, and further field dependent studies reveal the impact of contact hyperfine coupling on the dynamics of electron spins occupying distinct electronic states. Beyond above works, we also pursue optical detection of dynamic spin pumping in Fe/MgO/GaAs heterostructures in parallel. I will discuss the development and progress that we have made toward this goal. This project can be simply divided into two phases. In the first phase, we focused on microwave excitation and optical detection of spin pumping. In the second phase, we focused on all-optical excitation and detection of spin pumping. A number of measurement strategies have been developed and executed in both stages to hunt for a spin pumping signal. I will discuss the preliminary data based upon them.

Collective nuclear stabilization in single quantum dots by noncollinear hyperfine interaction

NASA Astrophysics Data System (ADS)

Yang, Wen; Sham, L. J.

2012-06-01

We present a theory of efficient suppression of the collective nuclear spin fluctuation, which prolongs the electron spin coherence time through the noncollinear hyperfine interaction between the nuclear spins and the hole spin. This provides a general paradigm to combat decoherence by direct control of environmental noise, and a possible solution to the puzzling observation of symmetric broadening of the absorption spectra in two recent experiments [Xu , Nature (London)NATUAS0028-083610.1038/nature08120 459, 1105 (2009) and Latta , Nature Phys.1745-247310.1038/nphys1363 5, 758 (2009)].

Control of coherence among the spins of a single electron and the three nearest neighbor {sup 13}C nuclei of a nitrogen-vacancy center in diamond

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

Shimo-Oka, T.; Miwa, S.; Suzuki, Y.

2015-04-13

Individual nuclear spins in diamond can be optically detected through hyperfine couplings with the electron spin of a single nitrogen-vacancy (NV) center; such nuclear spins have outstandingly long coherence times. Among the hyperfine couplings in the NV center, the nearest neighbor {sup 13}C nuclear spins have the largest coupling strength. Nearest neighbor {sup 13}C nuclear spins have the potential to perform fastest gate operations, providing highest fidelity in quantum computing. Herein, we report on the control of coherences in the NV center where all three nearest neighbor carbons are of the {sup 13}C isotope. Coherence among the three and fourmore » qubits are generated and analyzed at room temperature.« less

Development and characterization of Mn2+-doped MgO nanoparticles by solution combustion synthesis

NASA Astrophysics Data System (ADS)

Basha, Md. Hussain; Gopal, N. O.; Rao, J. L.; Nagabhushana, H.; Nagabhushana, B. M.; Chakradhar, R. P. S.

2015-06-01

Mn doped MgO Nanoparticles have been prepared by Solution Combustion Synthesis. The synthesized sample is characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and Electron Paramagnetic Resonance (EPR). The prepared MgO:Mn (1 mol%) nano crystals appear to be of simple cubic crystalline phase with lattice parameters a = 4.218(2) Å and cell volume = 74.98 (7) Å3. SEM micrograph of powders show highly porous, many agglomerates with irregular morphology, large voids, cracks and pores. EPR spectrum of the sample at room temperature exhibit an isotropic sextet hyperfine pattern, centered at g=1.99, characteristic if Mn2+ ions with S=I=5/2.The observed g value and the hyperfine value reveal the ionic bonding between Mn2+ and its surroundings.

Diode laser spectroscopy of the MnD radical ( 7Σ) and the determination of mass-independent parameters

NASA Astrophysics Data System (ADS)

Urban, Rolf-Dieter; Jones, Harold

1991-03-01

The infrared spectrum of the manganese deuteride radical has been observed in its ground electronic state ( 7Σ) using a diode-laser spectrometer. The hyperfine structure of a number of infrared transitions in the bands ν=1←0, ν=2←1 and ν=3←2 were measured with a nominal accuracy of ±0.001 cm -1. In all cases, the complete structure was easily resolved. Dunham parameters, spin—rotation and spin—spin coupling parameters were determined from the MnD data. A simultaneous fit of these data with those determined previously for MnH was carried out to determine mass-independent parameters and mass-scaling coefficients.

Modification of structural and magnetic properties of soft magnetic multi-component metallic glass by 80 MeV 16O6+ ion irradiation

NASA Astrophysics Data System (ADS)

Kane, S. N.; Shah, M.; Satalkar, M.; Gehlot, K.; Kulriya, P. K.; Avasthi, D. K.; Sinha, A. K.; Modak, S. S.; Ghodke, N. L.; Reddy, V. R.; Varga, L. K.

2016-07-01

Effect of 80 MeV 16O6+ ion irradiation in amorphous Fe77P8Si3C5Al2Ga1B4 alloy is reported. Electronic energy loss induced modifications in the structural and, magnetic properties were monitored by synchrotron X-ray diffraction (SXRD), Mössbauer and, magnetic measurements. Broad amorphous hump seen in SXRD patterns reveals the amorphous nature of the studied specimens. Mössbauer measurements suggest that: (a) alignment of atomic spins within ribbon plane, (b) changes in average hyperfine field suggests radiation-induced decrease in the inter atomic distance around Mössbauer (Fe) atom, (c) hyperfine field distribution confirms the presence of non-magnetic elements (e.g. - B, P, C) in the first near-neighbor shell of the Fe atom, thus reducing its magnetic moment, and (d) changes in isomer shift suggests variation in average number of the metalloid near neighbors and their distances. Minor changes in soft magnetic behavior - watt loss and, coercivity after an irradiation dose of 2 × 1013 ions/cm2 suggests prospective application of Fe77P8Si3C5Al2Ga1B4 alloy as core material in accelerators (radio frequency cavities).

Interface influence on the properties of Co90Fe10 films on soft magnetic underlayers - Magnetostrictive and Mössbauer spectrometry studies

NASA Astrophysics Data System (ADS)

Szumiata, Tadeusz; Gzik-Szumiata, Małgorzata; Brzózka, Katarzyna; Górka, Bogumił; Gawroński, Michał; Caruana Finkel, Anastasia; Reeves-McLaren, Nik; Morley, Nicola A.

2016-03-01

The main aim of the work was to show the correlation between magnetostrictive properties and microstructure of 25 nm thick Co90Fe10 films deposited on soft magnetic underlayers. A special attention was paid to the role of the interface region. In the case of Co90Fe10 on 25 nm and 35 nm thick METGLAS underlayers one can resolve in conversion electron Mössbauer spectra two hyperfine field distributions (high-field and medium-field ones) corresponding to both constituents of bilayers. Analogical distributions describe the spectra of Co90Fe10 on 25 nm and 35 nm thick Ni81Fe19 underlayers, however an additional low-field, smeared component has been observed. It has been attributed to the interface layer (of partially disordered structure) between magnetostrictive layer and soft magnetic layer. Such interpretation is backed up by the obtained strong correlation between mean hyperfine field value and magnetostriction constant of the films. The investigated bilayers are good candidates for MRAM devices.

First principles calculations of the magnetic and hyperfine properties of Fe/N/Fe and Fe/O/Fe multilayers in the ground state of cohesive energy

NASA Astrophysics Data System (ADS)

dos Santos, A. V.; Samudio Pérez, C. A.; Muenchen, D.; Anibele, T. P.

2015-01-01

The ground state properties of Fe/N/Fe and Fe/O/Fe multilayers were investigated using the first principles calculations. The calculations were performed using the Linearized Augmented Plane Wave (LAPW) method implemented in the Wien2k code. A supercell consisting of one layer of nitride (or oxide) between two layers of Fe in the bcc structure was used to model the structure of the multilayer. The research in new materials also stimulated theoretical and experimental studies of iron-based nitrides due to their variety of structural and magnetic properties for the potential applications as in high strength steels and for high corrosion resistance. It is obvious from many reports that magnetic iron nitrides such as γ-Fe4N and α-Fe16N2 have interesting magnetic properties, among these a high magnetisation saturation and a high density crimp. However, although Fe-N films and multilayers have many potential applications, they can be produced in many ways and are being extensively studied from the theoretical point of view there is no detailed knowledge of their electronic structure. Clearly, efforts to understand the influence of the nitrogen atoms on the entire electronic structure are needed as to correctly interpret the observed changes in the magnetic properties when going from Fe-N bulk compounds to multilayer structures. Nevertheless, the N atoms are not solely responsible for electronics alterations in solid compounds. Theoretical results showed that Fe4X bulk compounds, where X is a variable atom with increasing atomic number (Z), the nature of bonding between X and adjacent Fe atoms changes from more covalent to more ionic and the magnetic moments of Fe also increase for Z=7, i.e. N. This is an indicative that atoms with a Z number higher than 7, i.e., O, can produce several new alterations in the entire magnetic properties of Fe multilayers. This paper presents the first results of an ab-initio electronic structure calculations, performed for Fe-N and Fe-O multilayers. Firstly, the formation energy and the cohesive energy of the multilayers are discussed. For optimised values, the cohesive energy of the multilayers to obtain the lattice parameters at the equilibrium ground state was used, i.e. a new methodology for this calculus was applied. Secondly, the magnetic properties and hyperfine interactions (magnetic field, electric field gradient and the isomer shift) of the iron atoms of the multilayers are discussed.

POLARIZED SCATTERING OF LIGHT FOR ARBITRARY MAGNETIC FIELDS WITH LEVEL-CROSSINGS FROM THE COMBINATION OF HYPERFINE AND FINE STRUCTURE SPLITTINGS

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

Sowmya, K.; Nagendra, K. N.; Sampoorna, M.

2015-12-01

Interference between magnetic substates of the hyperfine structure states belonging to different fine structure states of the same term influences the polarization for some of the diagnostically important lines of the Sun's spectrum, like the sodium and lithium doublets. The polarization signatures of this combined interference contain information on the properties of the solar magnetic fields. Motivated by this, in the present paper, we study the problem of polarized scattering on a two-term atom with hyperfine structure by accounting for the partial redistribution in the photon frequencies arising due to the Doppler motions of the atoms. We consider the scatteringmore » atoms to be under the influence of a magnetic field of arbitrary strength and develop a formalism based on the Kramers–Heisenberg approach to calculate the scattering cross section for this process. We explore the rich polarization effects that arise from various level-crossings in the Paschen–Back regime in a single scattering case using the lithium atomic system as a concrete example that is relevant to the Sun.« less

Polaron spin echo envelope modulations in an organic semiconducting polymer

DOE PAGES

Mkhitaryan, V. V.; Dobrovitski, V. V.

2017-06-01

Here, we present a theoretical analysis of the electron spin echo envelope modulation (ESEEM) spectra of polarons in semiconducting π -conjugated polymers. We show that the contact hyperfine coupling and the dipolar interaction between the polaron and the proton spins give rise to different features in the ESEEM spectra. Our theory enables direct selective probe of different groups of nuclear spins, which affect the polaron spin dynamics. Namely, we demonstrate how the signal from the distant protons (coupled to the polaron spin via dipolar interactions) can be distinguished from the signal coming from the protons residing on the polaron sitemore » (coupled to the polaron spin via contact hyperfine interaction). We propose a method for directly probing the contact hyperfine interaction, that would enable detailed study of the polaron orbital state and its immediate environment. Lastly, we also analyze the decay of the spin echo modulation, and its connection to the polaron transport.« less

Proton, muon and ¹³C hyperfine coupling constants of C₆₀X and C₇₀X (X = H, Mu).

PubMed

Brodovitch, Jean-Claude; Addison-Jones, Brenda; Ghandi, Khashayar; McKenzie, Iain; Percival, Paul W

2015-01-21

The reaction of H atoms with fullerene C70 has been investigated by identifying the radical products formed by addition of the atom muonium (Mu) to the fullerene in solution. Four of the five possible radical isomers of C70Mu were detected by avoided level-crossing resonance (μLCR) spectroscopy, using a dilute solution of enriched (13)C70 in decalin. DFT calculations were used to predict muon and (13)C isotropic hyperfine constants as an aid to assigning the observed μLCR signals. Computational methods were benchmarked against previously published experimental data for (13)C60Mu in solution. Analysis of the μLCR spectrum resulted in the first experimental determination of (13)C hyperfine constants in either C70Mu or C70H. The large number of values confirms predictions that the four radical isomers have extended distributions of unpaired electron spin.

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

Laser Induced Optical Pumping Measurements of Cross Sections for Fine and Hyperfine Structure Transitions in Sodium Induced by Collisions with Helium Argon Atoms

NASA Technical Reports Server (NTRS)

Dobson, Chris C.; Sung, C. C.

1998-01-01

Optical pumping of the ground states of sodium can radically alter the shape of the laser induced fluorescence excitation spectrum, complicating measurements of temperature, pressure, etc., which are based on these spectra. Modeling of the fluorescence using rate equations for the eight hyperfine states of the sodium D manifolds can be used to quantify the contribution to the ground state pumping of transitions among the hyperfine excited states induced by collisions with buffer gas atoms. This model is used here to determine, from the shape of experimental spectra, cross sections for (Delta)F transitions of the P(sub 3/2) state induced by collisions with helium and argon atoms, for a range of values assumed for the P(sub 1/2), (Delta)F cross sections. The hyperfine cross sections measured using this method, which is thought to be novel, are compared with cross sections for transitions involving polarized magnetic substates, m(sub F), measured previously using polarization sensitive absorption. Also, fine structure transition ((Delta)J) cross sections were measured in the pumped vapor, giving agreement with previous measurements made in the absence of pumping.

Laser-Induced Optical Pumping Measurements of Cross Section for Fine- and Hyperfine-Structure Transitions in Sodium Induced by Collisions with Helium and Argon Atoms

NASA Technical Reports Server (NTRS)

Dobson, Chris C.; Sung, C. C.

1999-01-01

Optical pumping of the ground states of sodium can radically alter the shape of the laser-induced fluorescence excitation spectrum, complicating measurements of temperature, pressure, etc., which are based on these spectra. Modeling of the fluorescence using rate equations for the eight hyperfine states of the sodium D manifolds can be used to quantify the contribution to the ground state pumping of transitions among the hyperfine excited states induced by collisions with buffer gas atoms. This model is used here to determine, from the shape of experimental spectra, cross sections lor DELTA.F transitions of the P(sub 3/2) state induced by collisions with helium and argon atoms, for a range of values assumed for the P(sub 1/2), DELTA.F cross sections. The hyperfine cross sections measured using this method, which to our knowledge is novel, are compared with cross sections for transitions involving polarized magnetic substates m(sub F) measured previously using polarization sensitive absorption. Also, fine-structure transition cross sections were measured in the pumped vapor, giving agreement with previous measurements made in the absence of pumping.

Electron paramagnetic resonance studies on conformation states and metal ion exchange properties of vanadium bromoperoxidase

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

de Boer, E.; Boon, K.; Wever, R.

An electron paramagnetic resonance (EPR) study was carried out to examine structural aspects of vanadium-containing bromoperoxidase from the brown seaweed Ascophyllum nodosum. At high pH, the reduced form of bromoperoxidase showed an apparently axially symmetric EPR signal with 16 hyperfine lines. When the pH was lowered, a new EPR spectrum was formed. When EPR spectra of the reduced enzyme were recorded in the pH range from 4.2 to 8.4, it appeared that these changes were linked to a functional group with an apparent pK/sub a/ of about 5.4. In D/sub 2/O this value for the pK/sub a/ was 5.3. Itmore » is suggested that these effects arise from protonation of histidine or aspartate/glutamate residues near the metal ion. The values for the isotropic hyperfine coupling constant of the reduced enzyme at both high and low pH are also consistent with a ligand field containing nitrogen and/or oxygen donor atoms. When reduced bromoperoxidase was dissolved in D/sub 2/O or H/sub 2//sup 17/O instead of H/sub 2//sup 16/O, vanadium (IV) hyperfine line widths were markedly affected, demonstrating that water is a ligand of the metal ion. Together with previous work these findings suggest that vanadium (IV) is not involved in catalytic turnover and confirm the model in which the vanadium (V) ion of the native enzyme only serves to bind both hydrogen peroxide and bromide. After excess vanadate was added to a homogeneous preparation of purified bromoperoxidase, the extent of vanadium bound to the protein increased from 0.5 to 1.1, with a concomitant enhancement of enzymic activity. Finally, it is demonstrated that both vanadate (VO/sub 4//sup 3 -/) and molybdate (MoO/sub 4//sup 2 -/) compete for the same site on apobromoperoxidase.« less

Collisional relaxation of MnH (X7Σ+) in a magnetic field: effect of the nuclear spin of Mn.

PubMed

Stoecklin, T; Halvick, Ph

2011-11-14

In the present study we investigate the role played by the hyperfine structure of manganese in the cooling and magnetic trapping of MnH((7)Σ(+)). The effect of the hyperfine structure of Mn on the relaxation of the magnetically trappable maximally stretched low-field seeking state of MnH((7)Σ(+)) in collisions with (3)He is deduced from comparison between the results of the present approach and our previous nuclear spin free calculations. We show that our previous results are unchanged at the temperature of the buffer gas cooling experiment but find a new resonance at very low collision energy. The role played by the different contributions to the hyperfine diatomic Hamiltonian considered in this work as well as the effect of an applied magnetic field on this resonance are also analyzed.

Long-Lived Ultracold Molecules with Electric and Magnetic Dipole Moments.

PubMed

Rvachov, Timur M; Son, Hyungmok; Sommer, Ariel T; Ebadi, Sepehr; Park, Juliana J; Zwierlein, Martin W; Ketterle, Wolfgang; Jamison, Alan O

2017-10-06

We create fermionic dipolar ^{23}Na^{6}Li molecules in their triplet ground state from an ultracold mixture of ^{23}Na and ^{6}Li. Using magnetoassociation across a narrow Feshbach resonance followed by a two-photon stimulated Raman adiabatic passage to the triplet ground state, we produce 3×10^{4} ground state molecules in a spin-polarized state. We observe a lifetime of 4.6 s in an isolated molecular sample, approaching the p-wave universal rate limit. Electron spin resonance spectroscopy of the triplet state was used to determine the hyperfine structure of this previously unobserved molecular state.

Long-Lived Ultracold Molecules with Electric and Magnetic Dipole Moments

NASA Astrophysics Data System (ADS)

Rvachov, Timur M.; Son, Hyungmok; Sommer, Ariel T.; Ebadi, Sepehr; Park, Juliana J.; Zwierlein, Martin W.; Ketterle, Wolfgang; Jamison, Alan O.

2017-10-01

We create fermionic dipolar 23Na 6Li molecules in their triplet ground state from an ultracold mixture of 23Na and 6Li. Using magnetoassociation across a narrow Feshbach resonance followed by a two-photon stimulated Raman adiabatic passage to the triplet ground state, we produce 3 ×1 04 ground state molecules in a spin-polarized state. We observe a lifetime of 4.6 s in an isolated molecular sample, approaching the p -wave universal rate limit. Electron spin resonance spectroscopy of the triplet state was used to determine the hyperfine structure of this previously unobserved molecular state.

Chiral effective-field theory of the nucleon spin structure

NASA Astrophysics Data System (ADS)

Pascalutsa, Vladimir

2017-01-01

I will review the recent chiral EFT calculations of the nucleon (spin) structure functions at low Q2, confronted with the Jefferson Lab measurements. The moments of the structure functions correspond with various polarizabilities, and I will explain why one of them - δLT - is especially interesting. I will also discuss how the spin structure functions at low Q enter in the atomic calculations of the hyperfine splittings and how they are impacting the ongoing experimental program at PSI (Switzerland) to measure the ground-state hyperfine splitting of muonic hydrogen. Partially supported by the Deutsche Forschungsgemeinschaft (DFG) through the Collaborative Research Center SFB 1044 [The Low-Energy Frontier of the Standard Model].

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.

ESR lineshape and {sup 1}H spin-lattice relaxation dispersion in propylene glycol solutions of nitroxide radicals – Joint analysis

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

Kruk, D., E-mail: danuta.kruk@matman.uwm.edu.pl; Hoffmann, S. K.; Goslar, J.

2013-12-28

Electron Spin Resonance (ESR) spectroscopy and Nuclear Magnetic Relaxation Dispersion (NMRD) experiments are reported for propylene glycol solutions of the nitroxide radical: 4-oxo-TEMPO-d{sub 16} containing {sup 15}N and {sup 14}N isotopes. The NMRD experiments refer to {sup 1}H spin-lattice relaxation measurements in a broad frequency range (10 kHz–20 MHz). A joint analysis of the ESR and NMRD data is performed. The ESR lineshapes give access to the nitrogen hyperfine tensor components and the rotational correlation time of the paramagnetic molecule. The NMRD data are interpreted in terms of the theory of paramagnetic relaxation enhancement in solutions of nitroxide radicals, recentlymore » presented by Kruk et al. [J. Chem. Phys. 138, 124506 (2013)]. The theory includes the effect of the electron spin relaxation on the {sup 1}H relaxation of the solvent. The {sup 1}H relaxation is caused by dipole-dipole interactions between the electron spin of the radical and the proton spins of the solvent molecules. These interactions are modulated by three dynamic processes: relative translational dynamics of the involved molecules, molecular rotation, and electron spin relaxation. The sensitivity to rotation originates from the non-central positions of the interacting spin in the molecules. The electronic relaxation is assumed to stem from the electron spin–nitrogen spin hyperfine coupling, modulated by rotation of the radical molecule. For the interpretation of the NMRD data, we use the nitrogen hyperfine coupling tensor obtained from ESR and fit the other relevant parameters. The consistency of the unified analysis of ESR and NMRD, evaluated by the agreement between the rotational correlation times obtained from ESR and NMRD, respectively, and the agreement of the translation diffusion coefficients with literature values obtained for pure propylene glycol, is demonstrated to be satisfactory.« less

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.

Pulsed electron nuclear double resonance studies of the photoexcited triplet state of pentacene in p-terphenyl crystals at room temperature.

PubMed

Yago, Tomoaki; Link, Gerhard; Kothe, Gerd; Lin, Tien-Sung

2007-09-21

Pulsed electron nuclear double resonance (ENDOR) using a modified Davies-type [Phys. Lett. 47A, 1 (1974)] sequence is employed to study the hyperfine (HF) structure of the photoexcited triplet state of pentacene dispersed in protonated and deuterated p-terphenyl single crystals. The strong electron spin polarization and long phase memory time of triplet pentacene enable us to perform the ENDOR measurements on the S=1 spin system at room temperature. Proton HF tensor elements and spin density values of triplet pentacene are extracted from a detailed angular-dependent study in which the orientation of the magnetic field is varied systematically in two different pentacene planes. Analysis reveals that the pentacene molecule is no longer planar in the p-terphenyl host lattice. The distortion is more pronounced in the deuterated crystal where the unit cell dimensions are slightly smaller than those of the protonated crystal.

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.

Molecular beam electric resonance study of KCN, K 13CN and KC 15N

NASA Astrophysics Data System (ADS)

van Vaals, J. J.; Leo Meerts, W.; Dymanus, A.

1984-08-01

The microwave spectra of the isotopic species K 13CN and KC 15N have been investigated by molecular beam electric resonance spectroscopy, using the seeded beam technique. For both isotopic species about 20 rotational transitions originating in the ground vibrational state were observed in the frequency range 9-38 GHz. The observed transitions were fitted to an asymmetric rotor model to determine the three rotational, as well as the five quartic and three sextic centrifugal distortion constants. The hyperfine spectrum of KCN has been unravelled with the help of microwave-microwave double-resonance techniques. One hundred and forty hyperfine transitions in 11 rotational transitions have been assigned. The hyperfine structures of K 13CN and KC 15N were also studied. For all three isotopic species the quadrupole coupling constants and some spin-rotation coupling constants could be deduced. The rotational constants of the 13C and 15N isotopically substituted species of potassium cyanide, combined with those of the normal isotopic species (determined more accurately in this work), allowed an accurate and unambiguous evaluation of the structure, which was confirmed to be T shaped. Both the effective structure of the ground vibrational state and the substitution structure were evaluated. The results for the effective structural parameters are r CN = 1.169(3) Å, r KC = 2.716(9) Å, and r KN = 2.549(9) Å. The values obtained for the principal hyperfine coupling constant eQqz(N), the angle between the CN axis and zN, and the bond length rCN indicate that in gaseous potassium cyanide the CN group can be considered as an almost unperturbed CN - ion.

Energy, fine structure, hyperfine structure, and radiative transition rates of the high-lying multi-excited states for B-like neon

NASA Astrophysics Data System (ADS)

Zhang, Chun Mei; Chen, Chao; Sun, Yan; Gou, Bing Cong; Shao, Bin

2015-04-01

The Rayleigh-Ritz variational method with multiconfiguration interaction wave functions is used to obtain the energies of high-lying multi-excited quartet states 1 s 22 s2 pnl and 1 s 22 p 2 nl 4Pe,o ( n ≥ 2) in B-like neon, including the mass polarization and relativistic corrections. The fine structure and hyperfine structure of the excited quartet states for this system are investigated. Configuration structures of the high-lying multi-excited series are further identified by relativistic corrections and fine structure splittings. The transition rates and wavelengths are also calculated. Calculated wavelengths include the quantum electrodynamic effects. The results are compared with other theoretical and experimental data in the literature.

High-field Overhauser dynamic nuclear polarization in silicon below the metal-insulator transition.

PubMed

Dementyev, Anatoly E; Cory, David G; Ramanathan, Chandrasekhar

2011-04-21

Single crystal silicon is an excellent system to explore dynamic nuclear polarization (DNP), as it exhibits a continuum of properties from metallic to insulating as a function of doping concentration and temperature. At low doping concentrations DNP has been observed to occur via the solid effect, while at very high-doping concentrations an Overhauser mechanism is responsible. Here we report the hyperpolarization of (29)Si in n-doped silicon crystals, with doping concentrations in the range of (1-3) × 10(17) cm(-3). In this regime exchange interactions between donors become extremely important. The sign of the enhancement in our experiments and its frequency dependence suggest that the (29)Si spins are directly polarized by donor electrons via an Overhauser mechanism within exchange-coupled donor clusters. The exchange interaction between donors only needs to be larger than the silicon hyperfine interaction (typically much smaller than the donor hyperfine coupling) to enable this Overhauser mechanism. Nuclear polarization enhancement is observed for a range of donor clusters in which the exchange energy is comparable to the donor hyperfine interaction. The DNP dynamics are characterized by a single exponential time constant that depends on the microwave power, indicating that the Overhauser mechanism is a rate-limiting step. Since only about 2% of the silicon nuclei are located within 1 Bohr radius of the donor electron, nuclear spin diffusion is important in transferring the polarization to all the spins. However, the spin-diffusion time is much shorter than the Overhauser time due to the relatively weak silicon hyperfine coupling strength. In a 2.35 T magnetic field at 1.1 K, we observed a DNP enhancement of 244 ± 84 resulting in a silicon polarization of 10.4 ± 3.4% following 2 h of microwave irradiation.

Angular Distribution of Hyperfine Magnetic Field in Fe3O4 and Fe66Ni34 from Mössbauer Polarimetry

NASA Astrophysics Data System (ADS)

Szymański, K.; Satuła, D.; Dobrzyński, L.

2004-12-01

Experimental determination of some angular averages of hyperfine field is demonstrated. The averages relates to magnetic structure. Exemplary results of the measurements for Fe3O4 and Fe66Ni34 show that it is possible to obtain valuable information about the field magnitudes and orientations even when distributions of fields are present in the system under study.

[Hyperfine structure analysis in magnetic resonance spectroscopy: from astrophysical measurements towards endogenous biosensors in human tissue].

PubMed

Schröder, Leif

2007-01-01

The hyperfine interaction of two spins is a well studied effect in atomic systems. Magnetic resonance experiments demonstrate that the detectable dipole transitions are determined by the magnetic moments of the constituents and the external magnetic field. Transferring the corresponding quantum mechanics to molecular bound nuclear spins allows for precise prediction of NMR spectra obtained from metabolites in human tissue. This molecular hyperfine structure has been neglected so far in in vivo NMR spectroscopy but contains useful information, especially when studying molecular dynamics. This contribution represents a review of the concept of applying the Breit-Rabi formalism to coupled nuclear spins and discusses the immobilization of different metabolites in anisotropic tissue revealed by 1H NMR spectra of carnosine, phosphocreatine and taurine. Comparison of atomic and molecular spin systems allows for statements on the biological constraints for direct spin-spin interactions. Moreover, the relevance of hyperfine effects on the line shapes of multiplets of indirectly-coupled spin systems with more than two constituents can be predicted by analyzing quantum mechanical parameters. As an example, the superposition of eigenstates of the A MX system of adenosine 5'-triphosphate and its application for better quantification of 31P-NMR spectra will be discussed.

Manipulation of the spin memory of electrons in n-GaAs.

PubMed

Dzhioev, R I; Korenev, V L; Merkulov, I A; Zakharchenya, B P; Gammon, D; Efros, Al L; Katzer, D S

2002-06-24

We report on the optical manipulation of the electron spin relaxation time in a GaAs-based heterostructure. Experimental and theoretical study shows that the average electron spin relaxes through hyperfine interaction with the lattice nuclei, and that the rate can be controlled by electron-electron interactions. This time has been changed from 300 ns down to 5 ns by variation of the laser frequency. This modification originates in the optically induced depletion of an n-GaAs layer.

Pulsed-High Field/High-Frequency EPR Spectroscopy

NASA Astrophysics Data System (ADS)

Fuhs, Michael; Moebius, Klaus

Pulsed high-field/high-frequency electron paramagnetic resonance (EPR) spectroscopy is used to disentangle many kinds of different effects often obscured in continuous wave (cw) EPR spectra at lower magnetic fields/microwave frequencies. While the high magnetic field increases the resolution of G tensors and of nuclear Larmor frequencies, the high frequencies allow for higher time resolution for molecular dynamics as well as for transient paramagnetic intermediates studied with time-resolved EPR. Pulsed EPR methods are used for example for relaxation-time studies, and pulsed Electron Nuclear DOuble Resonance (ENDOR) is used to resolve unresolved hyperfine structure hidden in inhomogeneous linewidths. In the present article we introduce the basic concepts and selected applications to structure and mobility studies on electron transfer systems, reaction centers of photosynthesis as well as biomimetic models. The article concludes with an introduction to stochastic EPR which makes use of an other concept for investigating resonance systems in order to increase the excitation bandwidth of pulsed EPR. The limited excitation bandwidth of pulses at high frequency is one of the main limitations which, so far, made Fourier transform methods hardly feasible.

Rotation Dynamics Do Not Determine the Unexpected Isotropy of Methyl Radical EPR Spectra.

PubMed

Benetis, Nikolas P; Dmitriev, Yurij; Mocci, Francesca; Laaksonen, Aatto

2015-09-03

A simple first-principles electronic structure computation, further qc (quantum chemistry) computation, of the methyl radical gives three equal hf (hyperfine) couplings for the three protons with the unpaired electron. The corresponding dipolar tensors were notably rhombic and had different orientations and regular magnitude components, as they should, but what the overall A-tensor was seen by the electron spin is a different story! The final g = (2.002993, 2.002993, 2.002231) tensor and the hf coupling results obtained in vacuum, at the B3LYP/EPRIII level of theory clearly indicate that in particular the above A = (-65.19, -65.19, 62.54) MHz tensor was axial to a first approximation without considering any rotational dynamics for the CH3. This approximation was not applicable, however, for the trifluoromethyl CF3 radical, a heavier and nonplanar rotor with very anisotropic hf coupling, used here for comparison. Finally, a derivation is presented explaining why there is actually no need for the CH3 radicals to consider additional rotational dynamics in order for the electron to obtain an axially symmetric hf (hyperfine) tensor by considering the simultaneous dipolar couplings of the three protons. An additional consequence is an almost isotropic A-tensor for the electron spin of the CH3 radical. To the best of our knowledge, this point has not been discussed in the literature before. The unexpected isotropy of the EPR parameters of CH3 was solely attributed to the rotational dynamics and was not clearly separated from the overall symmetry of the species. The present theoretical results allowed a first explanation of the "forbidden" satellite lines in the CH3 EPR spectrum. The satellites are a fingerprint of the radical rotation, helping thus in distinguishing the CH3 reorientation from quantum rotation at very low temperatures.

Hyperfine Structure and Abundances of Heavy Elements in 68 Tauri (HD 27962)

NASA Astrophysics Data System (ADS)

Martinet, S.; Monier, R.

2017-12-01

HD 27962, also known as 68 Tauri, is a Chemically Peculiar Am star member of the Hyades Open Cluster in the local arm of the Galaxy. We have modeled the high resolution SOPHIE (R=75000) spectrum of 68 Tauri using updated model atmosphere and spectrum synthesis to derive chemical abundances in its atmosphere. In particular, we have studied the effect of the inclusion of Hyperfine Structure of various Baryum isotopes on the determination of the Baryum abundance in 68 Tauri. We have also derived new abundances using updated accurate atomic parameters retrieved from the NIST database.

ESR imaging investigations of two-phase systems.

PubMed

Herrmann, Werner; Stösser, Reinhard; Borchert, Hans-Hubert

2007-06-01

The possibilities of electron spin resonance (ESR) and electron spin resonance imaging (ESRI) for investigating the properties of the spin probes TEMPO and TEMPOL in two-phase systems have been examined in the systems water/n-octanol, Miglyol/Miglyol, and Precirol/Miglyol. Phases and regions of the phase boundary could be mapped successfully by means of the isotropic hyperfine coupling constants, and, moreover, the quantification of rotational and lateral diffusion of the spin probes was possible. For the quantitative treatment of the micropolarity, a simplified empirical model was established on the basis of the Nernst distribution and the experimentally determined isotropic hyperfine coupling constants. The model does not only describe the summarized micropolarities of coexisting phases, but also the region of the phase boundary, where solvent molecules of different polarities and tendencies to form hydrogen bonds compete to interact with the NO group of the spin probe. Copyright 2007 John Wiley & Sons, Ltd.

Delocalization of Coherent Triplet Excitons in Linear Rigid Rod Conjugated Oligomers.

PubMed

Hintze, Christian; Korf, Patrick; Degen, Frank; Schütze, Friederike; Mecking, Stefan; Steiner, Ulrich E; Drescher, Malte

2017-02-02

In this work, the triplet state delocalization in a series of monodisperse oligo(p-phenyleneethynylene)s (OPEs) is studied by pulsed electron paramagnetic resonance (EPR) and pulsed electron nuclear double resonance (ENDOR) determining zero-field splitting, optical spin polarization, and proton hyperfine couplings. Neither the zero-field splitting parameters nor the optical spin polarization change significantly with OPE chain length, in contrast to the hyperfine coupling constants, which showed a systematic decrease with chain length n according to a 2/(1 + n) decay law. The results provide striking evidence for the Frenkel-type nature of the triplet excitons exhibiting full coherent delocalization in the OPEs under investigation with up to five OPE repeat units and with a spin density distribution described by a nodeless particle in the box wave function. The same model is successfully applied to recently published data on π-conjugated porphyrin oligomers.

Development and characterization of Mn{sup 2+}-doped MgO nanoparticles by solution combustion synthesis

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

Basha, Md. Hussain; Gopal, N. O., E-mail: nogopal@yahoo.com; Rao, J. L.

2015-06-24

Mn doped MgO Nanoparticles have been prepared by Solution Combustion Synthesis. The synthesized sample is characterized by X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and Electron Paramagnetic Resonance (EPR). The prepared MgO:Mn (1 mol%) nano crystals appear to be of simple cubic crystalline phase with lattice parameters a = 4.218(2) Å and cell volume = 74.98 (7) Å{sup 3}. SEM micrograph of powders show highly porous, many agglomerates with irregular morphology, large voids, cracks and pores. EPR spectrum of the sample at room temperature exhibit an isotropic sextet hyperfine pattern, centered at g=1.99, characteristic if Mn{sup 2+} ions with S=I=5/2.The observedmore » g value and the hyperfine value reveal the ionic bonding between Mn{sup 2+} and its surroundings.« less

Revealing the Cu(2+) ions localization at low symmetry Bi sites in photorefractive Bi12GeO20 crystals doped with Cu and V by high frequency EPR.

PubMed

Nistor, Sergiu V; Stefan, Mariana; Goovaerts, Etienne; Ramaz, François; Briat, Bernard

2015-10-01

The sites of incorporation of Cu(2+) impurity ions in Bi12GeO20 single crystals co-doped with copper and vanadium have been investigated by electron paramagnetic resonance (EPR). While the X-band EPR spectra consist of a simple broad (ΔB ∼50 mT) line with anisotropic lineshape, the W-band EPR spectra exhibit well resolved, strongly anisotropic lines, due to transitions within the 3d(9)-(2)D ground manifold of the Cu(2+) ions. The most intense group of lines, attributed to the dominant Cu(2+)(I) center, displays a characteristic four components hyperfine structure for magnetic field orientations close to a 〈110〉 direction. The g and A tensor main axes are very close to one of the 12 possible sets of orthogonal 〈1-10〉, 〈00-1〉 and 〈110〉 crystal directions. Several less intense lines, with unresolved hyperfine structure and similar symmetry properties, mostly overlapped by the Cu(2+)(I) spectrum, were attributed to Cu(2+)(II) centers. The two paramagnetic centers are identified as substitutional Cu(2+) ions at Bi(3+) sites with low C1 symmetry, very likely resulting from different configurations of neighboring charge compensating defects. Copyright © 2015 Elsevier Inc. All rights reserved.

ISOTROPIC INELASTIC COLLISIONS IN A MULTITERM ATOM WITH HYPERFINE STRUCTURE

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

Belluzzi, Luca; Landi Degl’Innocenti, Egidio; Bueno, Javier Trujillo

2015-10-10

A correct modeling of the scattering polarization profiles observed in some spectral lines of diagnostic interest, the sodium doublet being one of the most important examples, requires taking hyperfine structure (HFS) and quantum interference between different J-levels into account. An atomic model suitable for taking these physical ingredients into account is the so-called multiterm atom with HFS. In this work, we introduce and study the transfer and relaxation rates due to isotropic inelastic collisions with electrons, which enter the statistical equilibrium equations (SEE) for the atomic density matrix of this atomic model. Under the hypothesis that the electron–atom interaction ismore » described by a dipolar operator, we provide useful relations between the rates describing the transfer and relaxation of quantum interference between different levels (whose numerical values are in most cases unknown) and the usual rates for the atomic level populations, for which experimental data and/or approximate theoretical expressions are generally available. For the particular case of a two-term atom with HFS, we present an analytical solution of the SEE for the spherical statistical tensors of the upper term, including both radiative and collisional processes, and we derive the expression of the emission coefficient in the four Stokes parameters. Finally, an illustrative application to the Na i D{sub 1} and D{sub 2} lines is presented.« less

Microstructure, hyperfine interaction and magnetic transition of Fe-25%Ni-5%Si-x%Co alloys

NASA Astrophysics Data System (ADS)

Gungunes, H.

2016-12-01

Morphological and magnetic properties in Fe-25%Ni-5%Si-x%Co (x = 0, 10, 15) alloys are investigated. Scanning electron microscopy (SEM), Mössbauer spectroscopy and AC magnetic susceptibility measurements are used to determine the physical properties of alloys. The martensite morphology changed depending on the Co content. The Mössbauer study shows that the volume fraction and hyperfine field of martensite increases while isomer shift values decrease with increasing Co content. On the other hand; AC susceptibility results showed that; Co is an effective element which can be used to control both the magnetic transition and martensitic transformation temperatures.

Angular distribution and polarization of X-ray radiation in highly charged He-like ions: hyperfine-induced transition

NASA Astrophysics Data System (ADS)

Chen, Zhan-Bin; Dong, Chen-Zhong

2018-06-01

The angular distribution and polarization properties of the X-rays produced by the hyperfine-induced transition are investigated within a fully relativistic distorted-wave approximation. The calculations are performed for the 1 s2 p 3/2 3P2 F i = 3/2 → 1 s 2 1S0 F f = 1/2 component of the Kα 1 decay for highly charged He-like 119Sn48+ and 207Tl79+ ions with nuclear spin I = 1/2 following impact excitations by an un-polarized and a completely longitudinally-polarized electron beam, respectively. The Breit interaction and mutipole mixing between the leading M2 decay and the hyperfine-induced E1 decay corrections to both linear and circular polarizations of the emitted X-ray radiations are evaluated. All these effects are found to be significant and may potentially explain the disagreement between the theories and experiments related to the polarization properties of the X-ray radiation.

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

van den Berg, R.; Brandino, G. P.; El Araby, O.

In this study, we introduce an integrability-based method enabling the study of semiconductor quantum dot models incorporating both the full hyperfine interaction as well as a mean-field treatment of dipole-dipole interactions in the nuclear spin bath. By performing free induction decay and spin echo simulations we characterize the combined effect of both types of interactions on the decoherence of the electron spin, for external fields ranging from low to high values. We show that for spin echo simulations the hyperfine interaction is the dominant source of decoherence at short times for low fields, and competes with the dipole-dipole interactions atmore » longer times. On the contrary, at high fields the main source of decay is due to the dipole-dipole interactions. In the latter regime an asymmetry in the echo is observed. Furthermore, the non-decaying fraction previously observed for zero field free induction decay simulations in quantum dots with only hyperfine interactions, is destroyed for longer times by the mean-field treatment of the dipolar interactions.« less

Competing interactions in semiconductor quantum dots

DOE PAGES

van den Berg, R.; Brandino, G. P.; El Araby, O.; ...

2014-10-14

In this study, we introduce an integrability-based method enabling the study of semiconductor quantum dot models incorporating both the full hyperfine interaction as well as a mean-field treatment of dipole-dipole interactions in the nuclear spin bath. By performing free induction decay and spin echo simulations we characterize the combined effect of both types of interactions on the decoherence of the electron spin, for external fields ranging from low to high values. We show that for spin echo simulations the hyperfine interaction is the dominant source of decoherence at short times for low fields, and competes with the dipole-dipole interactions atmore » longer times. On the contrary, at high fields the main source of decay is due to the dipole-dipole interactions. In the latter regime an asymmetry in the echo is observed. Furthermore, the non-decaying fraction previously observed for zero field free induction decay simulations in quantum dots with only hyperfine interactions, is destroyed for longer times by the mean-field treatment of the dipolar interactions.« less

Ro-vibrational averaging of the isotropic hyperfine coupling constant for the methyl radical

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

Adam, Ahmad Y.; Jensen, Per, E-mail: jensen@uni-wuppertal.de; Yachmenev, Andrey

2015-12-28

We present the first variational calculation of the isotropic hyperfine coupling constant of the carbon-13 atom in the CH{sub 3} radical for temperatures T = 0, 96, and 300 K. It is based on a newly calculated high level ab initio potential energy surface and hyperfine coupling constant surface of CH{sub 3} in the ground electronic state. The ro-vibrational energy levels, expectation values for the coupling constant, and its temperature dependence were calculated variationally by using the methods implemented in the computer program TROVE. Vibrational energies and vibrational and temperature effects for coupling constant are found to be in verymore » good agreement with the available experimental data. We found, in agreement with previous studies, that the vibrational effects constitute about 44% of the constant’s equilibrium value, originating mainly from the large amplitude out-of-plane bending motion and that the temperature effects play a minor role.« less

Atomic dark matter with hyperfine interactions

NASA Astrophysics Data System (ADS)

Boddy, Kimberly K.; Kaplinghat, Manoj; Kwa, Anna; Peter, Annika H. G.

2017-11-01

We consider dark matter as an analog of hydrogen in a secluded sector and study its astrophysical implications. The self interactions between dark matter particles include elastic scatterings as well as inelastic processes from hyperfine transitions. We show that for a dark hydrogen mass in the 10-100 GeV range and a dark fine-structure constant larger than 0.01, the self-interaction cross section has the right magnitude and velocity dependence to explain the low dark matter density cores seen in small galaxies while being consistent with all constraints from observations of galaxy clusters. Excitations to the hyperfine state and subsequent decays, however, may cause significant cooling losses and affect the evolution of low-mass halos. We also find minimum halo masses in the range of 103.5-107 M⊙, which are significantly larger than the typical predictions for weakly interacting dark matter models. This pattern of observables in structure formation is unique to this model, making it possible to determine the viability of hidden-sector hydrogen as a dark matter candidate.

Spin polarization of {sup 87}Rb atoms with ultranarrow linewidth diode laser: Numerical simulation

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

Wang, Z. G.; Interdisciplinary Center of Quantum Information, National University of Defense Technology, Changsha, 410073; College of Science, National University of Defense Technology, Changsha, 410073

2016-08-15

In order to polarize {sup 87}Rb vapor effectively with ultranarrow linewidth diode laser, we studied the polarization as a function of some parameters including buffer gas pressure and laser power. Moreover, we also discussed the methods which split or modulate the diode laser frequency so as to pump the two ground hyperfine levels efficiently. We obtained some useful results through numerical simulation. If the buffer gas pressure is so high that the hyperfine structure is unresolved, the polarization is insensitive to laser frequency at peak absorption point so frequency splitting and frequency modulation methods do not show improvement. At lowmore » pressure and laser power large enough, where the hyperfine structure is clearly resolved, frequency splitting and frequency modulation methods can increase polarization effectively. For laser diodes, frequency modulation is easily realized with current modulation, so this method is attractive since it does not add any other components in the pumping laser system.« less

Subpicosecond X rotations of atomic clock states

NASA Astrophysics Data System (ADS)

Song, Yunheung; Lee, Han-gyeol; Kim, Hyosub; Jo, Hanlae; Ahn, Jaewook

2018-05-01

We demonstrate subpicosecond-timescale population transfer between the pair of hyperfine ground states of atomic rubidium using a single laser-pulse. Our scheme utilizes the geometric and dynamic phases induced during Rabi oscillation through the fine-structure excited state to construct an X rotation gate for the hyperfine-state qubit system. The experiment performed with a femtosecond laser and cold rubidium atoms, in a magnetooptical trap, shows over 98% maximal population transfer between the clock states.

Laser ablated hydantoin: A high resolution rotational study.

PubMed

Alonso, Elena R; Kolesniková, Lucie; Alonso, José L

2017-09-28

Laser ablation techniques coupled with broadband and narrowband Fourier transform microwave spectroscopies have allowed the high resolution rotational study of solid hydantoin, an important target in astrochemistry as a possible precursor of glycine. The complicated hyperfine structure arising from the presence of two 14 N nuclei in non-equivalent positions has been resolved and interpreted in terms of the nuclear quadrupole coupling interactions. The results reported in this work provide a solid base for the interstellar searches of hydantoin in the astrophysical surveys. The values of the nuclear quadrupole coupling constants have been also discussed in terms of the electronic environment around the respective nitrogen atom.

Density functional calculations of the Mössbauer parameters in hexagonal ferrite SrFe12O19

NASA Astrophysics Data System (ADS)

Ikeno, Hidekazu

2018-03-01

Mössbauer parameters in a magnetoplumbite-type hexagonal ferrite, SrFe12O19, are computed using the all-electron band structure calculation based on the density functional theory. The theoretical isomer shift and quadrupole splitting are consistent with experimentally obtained values. The absolute values of hyperfine splitting parameters are found to be underestimated, but the relative scale can be reproduced. The present results validate the site-dependence of Mössbauer parameters obtained by analyzing experimental spectra of hexagonal ferrites. The results also show the usefulness of theoretical calculations for increasing the reliability of interpretation of the Mössbauer spectra.

Laser-stimulated electric quadrupole transitions in the molecular hydrogen ion H2+

NASA Astrophysics Data System (ADS)

Korobov, V. I.; Danev, P.; Bakalov, D.; Schiller, S.

2018-03-01

Molecular hydrogen ions are of metrological relevance due to the possibility of precise theoretical evaluation of their spectrum and of external-field-induced shifts. We report the results of the calculations of the rate of laser-induced electric quadrupole transitions between a large set of ro-vibrational states of H2+. The hyperfine and Zeeman structure of the E 2 transition spectrum and the effects of the laser polarization are treated in detail. The treatment is generally applicable to molecules in 2Σ states. We also present the nuclear spin-electron spin-coupling constants, computed with a precision ten times higher than previously obtained.

Spin noise spectroscopy of ZnO

NASA Astrophysics Data System (ADS)

Horn, H.; Berski, F.; Balocchi, A.; Marie, X.; Mansur-Al-Suleiman, M.; Bakin, A.; Waag, A.; Hübner, J.; Oestreich, M.

2013-12-01

We investigate the thermal equilibrium dynamics of electron spins bound to donors in nanoporous ZnO by optical spin noise spectroscopy. The spin noise spectra reveal two noise contributions: A weak spin noise signal from undisturbed localized donor electrons with a dephasing time of 24 ns due to hyperfine interaction and a strong spin noise signal with a spin dephasing time of 5 ns which we attribute to localized donor electrons which interact with lattice defects.

Electron electric dipole moment and hyperfine interaction constants for ThO

NASA Astrophysics Data System (ADS)

Fleig, Timo; Nayak, Malaya K.

2014-06-01

A recently implemented relativistic four-component configuration interaction approach to study P- and T-odd interaction constants in atoms and molecules is employed to determine the electron electric dipole moment effective electric field in the Ω=1 first excited state of the ThO molecule. We obtain a value of Eeff=75.2GV/cm with an estimated error bar of 3% and 10% smaller than a previously reported result (Skripnikov et al., 2013). Using the same wavefunction model we obtain an excitation energy of TvΩ=1=5410 (cm), in accord with the experimental value within 2%. In addition, we report the implementation of the magnetic hyperfine interaction constant A|| as an expectation value, resulting in A||=-1339 (MHz) for the Ω=1 state in ThO. The smaller effective electric field increases the previously determined upper bound (Baron et al., 2014) on the electron electric dipole moment to |de|<9.7×10-29e cm and thus mildly mitigates constraints to possible extensions of the Standard Model of particle physics.

Electrical control of single hole spins in nanowire quantum dots.

PubMed

Pribiag, V S; Nadj-Perge, S; Frolov, S M; van den Berg, J W G; van Weperen, I; Plissard, S R; Bakkers, E P A M; Kouwenhoven, L P

2013-03-01

The development of viable quantum computation devices will require the ability to preserve the coherence of quantum bits (qubits). Single electron spins in semiconductor quantum dots are a versatile platform for quantum information processing, but controlling decoherence remains a considerable challenge. Hole spins in III-V semiconductors have unique properties, such as a strong spin-orbit interaction and weak coupling to nuclear spins, and therefore, have the potential for enhanced spin control and longer coherence times. A weaker hyperfine interaction has previously been reported in self-assembled quantum dots using quantum optics techniques, but the development of hole-spin-based electronic devices in conventional III-V heterostructures has been limited by fabrication challenges. Here, we show that gate-tunable hole quantum dots can be formed in InSb nanowires and used to demonstrate Pauli spin blockade and electrical control of single hole spins. The devices are fully tunable between hole and electron quantum dots, which allows the hyperfine interaction strengths, g-factors and spin blockade anisotropies to be compared directly in the two regimes.

Influence of the nuclear Zeeman effect on mode locking in pulsed semiconductor quantum dots

NASA Astrophysics Data System (ADS)

Beugeling, Wouter; Uhrig, Götz S.; Anders, Frithjof B.

2017-09-01

The coherence of the electron spin in a semiconductor quantum dot is strongly enhanced by mode locking through nuclear focusing, where the synchronization of the electron spin to periodic pulsing is slowly transferred to the nuclear spins of the semiconductor material, mediated by the hyperfine interaction between these. The external magnetic field that drives the Larmor oscillations of the electron spin also subjects the nuclear spins to a Zeeman-like coupling, albeit a much weaker one. For typical magnetic fields used in experiments, the energy scale of the nuclear Zeeman effect is comparable to that of the hyperfine interaction, so that it is not negligible. In this work, we analyze the influence of the nuclear Zeeman effect on mode locking quantitatively. Within a perturbative framework, we calculate the Overhauser-field distribution after a prolonged period of pulsing. We find that the nuclear Zeeman effect can exchange resonant and nonresonant frequencies. We distinguish between models with a single type and with multiple types of nuclei. For the latter case, the positions of the resonances depend on the individual g factors, rather than on the average value.

Modulated magnetic structure of F e3P O7 as seen by 57Fe Mössbauer spectroscopy

NASA Astrophysics Data System (ADS)

Sobolev, A. V.; Akulenko, A. A.; Glazkova, I. S.; Pankratov, D. A.; Presniakov, I. A.

2018-03-01

The paper reports results of the 57Fe Mössbauer measurements on an F e3P O4O3 powder sample recorded at various temperatures, including the point of magnetic phase transition TN≈163 K . The spectra measured above TN consist of a quadrupole doublet with high quadrupole splitting of Δ300 K≈1.10 mm /s , emphasizing that F e3 + ions are located in crystal positions with a strong electric-field gradient (EFG). To predict the sign and orientation of the main components of the EFG tensor, we calculated the EFG using the density-functional-theory approach. In the temperature range T

Discriminating the structure of exo-2-aminonorbornane using nuclear quadrupole coupling interactions.

PubMed

Écija, Patricia; Cocinero, Emilio J; Lesarri, Alberto; Millán, Judith; Basterretxea, Francisco; Fernández, José A; Castaño, Fernando

2011-04-28

The intrinsic conformational and structural properties of the bicycle exo-2-aminonorbornane have been probed in a supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy and quantum chemical calculations. The rotational spectrum revealed two different conformers arising from the internal rotation of the amino group, exhibiting small (MHz) hyperfine patterns originated by the (14)N nuclear quadrupole coupling interaction. Complementary ab initio (MP2) and DFT (B3LYP and M05-2X) calculations provided comparative predictions for the structural properties, rotational and centrifugal distortion data, hyperfine parameters, and isomerization barriers. Due to the similarity of the rotational constants, the structural assignment of the observed rotamers and the calculation of the torsion angles of the amino group were based on the conformational dependence of the (14)N nuclear quadrupole coupling hyperfine tensor. In the most stable conformation (ss), the two amino N-H bonds are staggered with respect to the adjacent C-H bond. In the second conformer (st), only one of the N-H bonds is staggered and the other is trans. A third predicted conformer (ts) was not detected, consistent with a predicted conformational relaxation to conformer ss through a low barrier of 5.2 kJ mol(-1).

Time-resolved ESR spectra of the α-hydroxybenzyl-amine complex

NASA Astrophysics Data System (ADS)

Kawai, Akio; Kobori, Yasuhiro; Obi, Kinichi

1993-11-01

Time-resolved ESR spectra of the α-hydroxybenzyl radical were measured in benzene and 2-propanol solutions by the photo-dissociation of benzoin. The hyperfine structure (hfs) of α-hydroxybenzyl depends on the solvents. In a benzene solution containing triethylamine, two species with different hyperfine structure appeared simultaneously. As the ratio of intensity for the two species depends on the concentration of triethylamine, one of them is assigned to the bare α-hydroxybenzyl and the other to the 1:1 complex of α-hydroxybenzyl and triethylamine. The equilibrium constant of complex formation was estimated to be about 450 M -1 from the analysis of CIDEP intensities.

Theory of the n = 2 levels in muonic helium-3 ions

NASA Astrophysics Data System (ADS)

Franke, Beatrice; Krauth, Julian J.; Antognini, Aldo; Diepold, Marc; Kottmann, Franz; Pohl, Randolf

2017-12-01

The present knowledge of Lamb shift, fine-, and hyperfine structure of the 2S and 2P states in muonic helium-3 ions is reviewed in anticipation of the results of a first measurement of several 2S → 2P transition frequencies in the muonic helium-3 ion, μ3He+. This ion is the bound state of a single negative muon μ- and a bare helium-3 nucleus (helion), 3He++. A term-by-term comparison of all available sources, including new, updated, and so far unpublished calculations, reveals reliable values and uncertainties of the QED and nuclear structure-dependent contributions to the Lamb shift and the hyperfine splitting. These values are essential for the determination of the helion rms charge radius and the nuclear structure effects to the hyperfine splitting in μ3He+. With this review we continue our series of theory summaries in light muonic atoms [see A. Antognini et al., Ann. Phys. 331, 127 (2013); J.J. Krauth et al., Ann. Phys. 366, 168 (2016); and M. Diepold et al. arXiv:1606.05231 (2016)].

Hyperfine Structure in the Pure Rotational Spectrum of 208Pb35Cl

NASA Astrophysics Data System (ADS)

Dewberry, Christopher T.; Grubbs, Garry S., II; Etchison, Kerry C.; Cooke, Stephen A.

2010-06-01

Initially in our laboratory the pure rotational spectrum of the title molecule was studied using a Balle-Flygare Fourier transform microwave spectrometer. Analysis was troublesome and so the spectrum was remeasured using a chirped pulse Fourier transform microwave (CP-FTMW) spectrometer. The correct intensity aspect of the CP-FTMW experiment allowed successful quantum number assignments for the hyperfine structure for the correct isotopologue. Spectroscopic constants have been obtained from a fit to a data set consisting of our measurements combined with those of a prior study on the X_2^2Π3/2 → X_1^2Π_{1/2 fine structure transitions. K. Ziebarth, K. D. Setzer, O. Shestakov and E. H. Fink J. Mol. Spectrosc., 191 108, 1998.

Calculated hyperfine coupling constants for 5,5-dimethyl-1-pyrroline N-oxide radical products in water and benzene

NASA Astrophysics Data System (ADS)

Nardali, Ş.; Ucun, F.; Karakaya, M.

2017-11-01

The optimized structures of some radical adducts of 5,5-dimethyl-1-pyrroline N-oxide were computed by different methods on ESR spectra. As trapped radicals, H, N3, NH2, CH3, CCl3, OOH in water and F, OH, CF3, CH2OH, OC2H5 in benzene solutions were used. The calculated isotropic hyperfine coupling constants of all the trapped radicals were compared with the corresponding experimental data. The hyperfine coupling constant due to the β proton of the nitroxide radical was seen to be consist with the McConnel's relation αβ = B 0 + B 1cos2θ and, to be effected with the opposite spin density of oxygen nucleus bonded to the nitrogen. It was concluded that in hyperfine calculations the DFT(B3PW91)/LanL2DZ level is superior computational quantum model relative to the used other level. Also, the study has been enriched by the computational of the optimized geometrical parameters, the hyper conjugative interaction energies, the atomic charges and spin densities for all the radical adducts.

Corrections to hyperfine splitting and Lamb shift induced by diagrams with second order radiative insertions in the electron line

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

Eides, M.I.; Karshenboim, S.G.; Shelyuto, V.A.

1994-12-31

Contributions to HFS and to the Lamb shift intervals of order a{sup 2}(Za){sup 5} induced by gauge invariant set of nineteen topologically different graphs with two radiative photons inserted in the electron line are considered. Corrections both to HFS and Lamb shift induced by nine diagrams are calculated in the Fried-Yennie gauge.

Coherent manipulation of an NV center and one carbon nuclear spin

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

Scharfenberger, Burkhard; Nemoto, Kae; Munro, William J.

2014-12-04

We study a three-qubit system formed by the NV center’s electronic and nuclear spin plus an adjacent spin 1/2 carbon {sup 13}C. Specifically, we propose a manipulation scheme utilizing the hyperfine coupling of the effective S=1 degree of freedom of the vacancy electrons to the two adjacent nuclear spins to achieve accurate coherent control of all three qubits.

The Hyperfine Structure of the Ground State in the Muonic Helium Atoms

NASA Astrophysics Data System (ADS)

Aznabayev, D. T.; Bekbaev, A. K.; Korobov, V. I.

2018-05-01

Non-relativistic ionization energies 3He2+μ-e- and 4He2+μ-e- of helium-muonic atoms are calculated for ground states. The calculations are based on the variational method of the exponential expansion. Convergence of the variational energies is studied by an increasing of a number of the basis functions N. This allows to claim that the obtained energy values have 26 significant digits for ground states. With the obtained results we calculate hyperfine splitting of the muonic helium atoms.

Structural and magnetic study of Al{sup 3+} doped Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4} nanoferrites

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

Wang, L.; Rai, B.K.; Mishra, S.R.

2015-05-15

Graphical abstract: Hyperfine field of individual sites (inset) and weighted average hyperfine field as a function of Al{sup 3+} content for Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4}. - Highlights: • Grain size reduction with Al{sup 3+} substitution. • Preferred occupancy of Al{sup 3+} at B site for higher Al{sup 3+} content. • Reduction in Ms, Tc, and hyperfine field with increasing Al{sup 3+} content. • Size dependent variation in coercivity. • Changes in isomer shift due to competing effect of volume and substitution. - Abstract: Nanostructured Al{sup 3+} doped Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4} (x = 0.0, 0.2, 0.4,more » 0.6, 0.8, and 1.0) ferrites were synthesized via the wet chemical method. X-ray diffraction, transmission electron microscopy, and magnetization measurements have been used to investigate the structural and magnetic properties of spinel ferrites calcined at 950 °C. With the doping of Al{sup 3+}, the particle size of Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4} first increased to 47 nm at x = 0.4 and then decreased down to 37 nm at x = 1. The main two absorption bands in IR spectra were observed around 600 cm{sup −1} and 400 cm{sup −1} corresponding to stretching vibration of tetrahedral and octahedral group Fe{sup 3+}–O{sup 2−}. Saturation magnetization and hyperfine field values decreased linearly with Al{sup 3+} due to magnetic dilution and the relative strengths of Fe–O–Me (Me = Fe, Ni, Zn, and Al) superexchanges. The coercive field showed an inverse dependence on ferrite particle size with minimum value of 82 Oe for x = 0.4. A continuous drop in Curie temperature was observed with the Al{sup 3+} substitution. From the Moessbauer spectral analysis and X-ray diffraction analysis, it is deduced that Al{sup 3+} for x < 0.4 has no obvious preference for either tetrahedral or octahedral site but has a greater preference for the B site for x > 0.4. In nutshell the study presents detailed structural and magnetic, and Moessbauer analysis of Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4} ferrites.« less

X-ray Crystallographic, Multifrequency Electron Paramagnetic Resonance, and Density Functional Theory Characterization of the Ni(P(Cy)2N(tBu)2)2(n+) Hydrogen Oxidation Catalyst in the Ni(I) Oxidation State.

PubMed

Niklas, Jens; Westwood, Mark; Mardis, Kristy L; Brown, Tiara L; Pitts-McCoy, Anthony M; Hopkins, Michael D; Poluektov, Oleg G

2015-07-06

The Ni(I) hydrogen oxidation catalyst [Ni(P(Cy)2N(tBu)2)2](+) (1(+); P(Cy)2N(tBu)2 = 1,5-di(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane) has been studied using a combination of electron paramagnetic resonance (EPR) techniques (X-, Q-, and D-band, electron-nuclear double resonance, hyperfine sublevel correlation spectroscopy), X-ray crystallography, and density functional theory (DFT) calculations. Crystallographic and DFT studies indicate that the molecular structure of 1(+) is highly symmetrical. EPR spectroscopy has allowed determination of the electronic g tensor and the spin density distribution on the ligands, and revealed that the Ni(I) center does not interact strongly with the potentially coordinating solvents acetonitrile and butyronitrile. The EPR spectra and magnetic parameters of 1(+) are found to be distinctly different from those for the related compound [Ni(P(Ph)2N(Ph)2)2](+) (4(+)). One significant contributor to these differences is that the molecular structure of 4(+) is unsymmetrical, unlike that of 1(+). DFT calculations on derivatives in which the R and R' groups are systematically varied have allowed elucidation of structure/substituent relationships and their corresponding influence on the magnetic resonance parameters.

Hyperfine field and magnetic structure in the B phase of CeCoIn5

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

Graf, Matthias J; Curro, Nicholas J; Young, Ben - Li

2009-01-01

We re-analyze Nuclear Magnetic Resonance (NMR) spectra observed at low temperatures and high magnetic fields in the field-induced B-phase of CeCoIn{sub 5}. The NMR spectra are consistent with incommensurate antiferromagnetic order of the Ce magnetic moments. However, we find that the spectra of the In(2) sites depend critically on the direction of the ordered moments, the ordering wavevector and the symmetry of the hyperfine coupling to the Ce spins. Assuming isotropic hyperfine coupling, the NMR spectra observed for H {parallel} [100] are consistent with magnetic order with wavevector Q = {pi}(1+{delta}/a, 1/a, 1/c) and Ce moments ordered antiferromagnetically along themore » [100] direction in real space. If the hyperfine coupling has dipolar symmetry, then the NMR spectra require Ce moments along the [001] direction. The dipolar scenario is also consistent with recent neutron scattering measurements that find an ordered moment of 0.15{micro}{sub B} along [001] and Q{sub n} = {pi}(1+{delta}/a, 1+{delta}c, 1/c) with incommensuration {delta} = 0.12 for field H {parallel} [1{bar 1}0]. Using these parameters, we find that the hyperfine field is consistent with both experiments. We speculate that the B phase of CeCoIn{sub 5} represents an intrinsic phase of modulated superconductivity and antiferromagnetism that can only emerge in a highly clean system.« less

Hyperfine interaction constants of 14NO2 in 14 500-16 800 cm-1 energy region

NASA Astrophysics Data System (ADS)

Tada, Kohei; Hirata, Michihiro; Kasahara, Shunji

2017-10-01

We observed hyperfine-resolved high-resolution fluorescence excitation spectra of k = 0, N = 1 ← 0 transitions in 82 vibronic bands of the à 2B2 ← X ˜ 2A1 system of 14NO2 in the 14 500-16 800 cm-1 region by crossing a jet-cooled molecular beam and a single-mode dye laser beam at right angles. We determined hyperfine interaction constants of the lower and upper states for all the observed vibronic bands based on the analysis of the hyperfine structures of k = 0, N = 1 ← 0 transitions. Most of the determined Fermi contact interaction constants were found to be distributed in 0.0013-0.0038 cm-1, which are intermediate in magnitude between those in lower and higher energy region reported by other groups. A sharp decreasing of the Fermi contact interaction constant was found in 16 200-16 600 cm-1, and it may be caused by the interaction with the dark C ˜ 2A2 state. The hyperfine interaction constants are powerful clues to obtain reliable vibronic assignment. We tentatively assigned vibronic bands located at 14 836 cm-1, 15 586 cm-1, and 16 322 cm-1 as the transitions to the intrinsic (0,7,0), (0,8,0), and (0,9,0) vibrational levels of the à 2B2 state, respectively.

Hyperfine structure and isotope shift of /sup 208/Bi in the 3067-A resonance line

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

Lamontagne, J.J.

1982-01-01

The hyperfine structure of /sup 208/Bi (I = 5) was measured using the 3067 A spectral line from the 6p/sup 2/7s (/sup 4/P/sub 1/2/) - 6p/sup 3/ (/sup 4/S/sub 3/2/) transition. After production of the isotope at the Princeton University Cyclotron, chemical separation, and mass separation, some 10/sup 12/ atoms were used to produce an absorption spectrum. The monochromator, Czerny-Turner design), had a 9.1 m focal length with a 25 cm diffraction grating used in autocollimation near 63/sup 0/. The spectrum was recorded on photographic plates. Measurements were made of the position of the components. From these the value /supmore » 208/A (/sup 4/P/sub 1/2) = 166 (1.5) mK was obtained. Neglecting hyperfine anomalies this gives /sup 208/A (/sup 4/S/sub 3/2/) = 15.07 (.1). The isotope shift /sup 208/Bi-/sup 208/Bi was measured to be 50.58 (7.5) mK.« less

Identification of the substrate radical intermediate derived from ethanolamine during catalysis by ethanolamine ammonia-lyase.

PubMed

Bender, Güneş; Poyner, Russell R; Reed, George H

2008-10-28

Rapid-mix freeze-quench (RMFQ) methods and electron paramagnetic resonance (EPR) spectroscopy have been used to characterize the steady-state radical in the deamination of ethanolamine catalyzed by adenosylcobalamin (AdoCbl)-dependent ethanolamine ammonia-lyase (EAL). EPR spectra of the radical intermediates formed with the substrates, [1-13C]ethanolamine, [2-13C]ethanolamine, and unlabeled ethanolamine were acquired using RMFQ trapping methods from 10 ms to completion of the reaction. Resolved 13C hyperfine splitting in EPR spectra of samples prepared with [1-13C]ethanolamine and the absence of such splitting in spectra of samples prepared with [2-13C]ethanolamine show that the unpaired electron is localized on C1 (the carbinol carbon) of the substrate. The 13C splitting from C1 persists from 10 ms throughout the time course of substrate turnover, and there was no evidence of a detectable amount of a product like radical having unpaired spin on C2. These results correct an earlier assignment for this radical intermediate [Warncke, K., et al. (1999) J. Am. Chem. Soc. 121, 10522-10528]. The EPR signals of the substrate radical intermediate are altered by electron spin coupling to the other paramagnetic species, cob(II)alamin, in the active site. The dipole-dipole and exchange interactions as well as the 1-13C hyperfine splitting tensor were analyzed via spectral simulations. The sign of the isotropic exchange interaction indicates a weak ferromagnetic coupling of the two unpaired electrons. A Co2+-radical distance of 8.7 A was obtained from the magnitude of the dipole-dipole interaction. The orientation of the principal axes of the 13C hyperfine splitting tensor shows that the long axis of the spin-bearing p orbital on C1 of the substrate radical makes an angle of approximately 98 degrees with the unique axis of the d(z2) orbital of Co2+.

Magnetoelectroluminescence of organic heterostructures: Analytical theory and spectrally resolved measurements

NASA Astrophysics Data System (ADS)

Liu, Feilong; Kelley, Megan R.; Crooker, Scott A.; Nie, Wanyi; Mohite, Aditya D.; Ruden, P. Paul; Smith, Darryl L.

2014-12-01

The effect of a magnetic field on the electroluminescence of organic light emitting devices originates from the hyperfine interaction between the electron/hole polarons and the hydrogen nuclei of the host molecules. In this paper, we present an analytical theory of magnetoelectroluminescence for organic semiconductors. To be specific, we focus on bilayer heterostructure devices. In the case we are considering, light generation at the interface of the donor and acceptor layers results from the formation and recombination of exciplexes. The spin physics is described by a stochastic Liouville equation for the electron/hole spin density matrix. By finding the steady-state analytical solution using Bloch-Wangsness-Redfield theory, we explore how the singlet/triplet exciplex ratio is affected by the hyperfine interaction strength and by the external magnetic field. To validate the theory, spectrally resolved electroluminescence experiments on BPhen/m-MTDATA devices are analyzed. With increasing emission wavelength, the width of the magnetic field modulation curve of the electroluminescence increases while its depth decreases. These observations are consistent with the model.

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.

Technology for On-Chip Qubit Control with Microfabricated Surface Ion Traps

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

Highstrete, Clark; Scott, Sean Michael; Nordquist, Christopher D.

2013-11-01

Trapped atomic ions are a leading physical system for quantum information processing. However, scalability and operational fidelity remain limiting technical issues often associated with optical qubit control. One promising approach is to develop on-chip microwave electronic control of ion qubits based on the atomic hyperfine interaction. This project developed expertise and capabilities at Sandia toward on-chip electronic qubit control in a scalable architecture. The project developed a foundation of laboratory capabilities, including trapping the 171Yb + hyperfine ion qubit and developing an experimental microwave coherent control capability. Additionally, the project investigated the integration of microwave device elements with surface ionmore » traps utilizing Sandia’s state-of-the-art MEMS microfabrication processing. This effort culminated in a device design for a multi-purpose ion trap experimental platform for investigating on-chip microwave qubit control, laying the groundwork for further funded R&D to develop on-chip microwave qubit control in an architecture that is suitable to engineering development.« less

Hyperfine interaction in K 2Ba[Fe(NO 2) 6

NASA Astrophysics Data System (ADS)

Padmakumar, K.; Manoharan, P. T.

2000-04-01

Magnetic hyperfine splitting observed in the low temperature Mössbauer spectrum of potassium barium hexanitro ferrate(II), in the absence of any external field, is attributed to the 5T 2g state of the central metal atom further split into a ground 5E g state and a first excited 5B 2g state under a distorted octahedral symmetry in contrast to the earlier prediction of 1A 1g ground state on the basis of room temperature Mössbauer spectral and other properties. The central iron atom is co-ordianted to six nitrito groups (NO 2-), having an oxidation state of +2. The temperature dependence of Mössbauer spectra is explained on the basis of electronic relaxation among the spin-orbit coupled levels of the 5E g ground state. Various kinds of electronic relaxation mechanisms have been compared to explain the proposed mechanism. The observed temperature dependent spectra with varying internal magnetic field and line width can be explained by simple spin lattice relaxation.

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

Herojit Singh, L.; Govindaraj, R., E-mail: govind@igcar.gov.in; Rajagopalan, S.

Mössbauer spectroscopic studies have been carried out at different temperatures across ferromagnetic to paramagnetic transition in Ni{sub 50}Fe{sub 35}Co{sub 15} and the evolution of hyperfine parameters such as centre shift and magnetic hyperfine fields with temperature has been studied. Mössbauer spectrum obtained at 300 K in Ni{sub 50}Fe{sub 35}Co{sub 15} exhibiting fcc crystal structure is a six line pattern with the mean value of the hyperfine field close to 33 Tesla. Ferromagnetic to paramagnetic transition has been observed to occur in this system around 895 K matching with that of magnetization results. Debye temperature of this nickel rich alloy ismore » deduced to be around 470 K matching with that of Ni. Effect of prolonged annealing at 750 K on the magnetic property is also investigated with respect to the thermal stability of the alloy.« less

EPR Spectroscopy of Radical Ions of a 2,3-Diamino-1,4-naphthoquinone Derivative.

PubMed

Tarábek, Ján; Wen, Jin; Dron, Paul I; Pospíšil, Lubomír; Michl, Josef

2018-05-18

We report the electron paramagnetic resonance spectra of the radical cation and radical anion of 1,2,2,3-tetramethyl-2,3-dihydro-1 H-naphtho[2,3- d]imidazole-4,9-dione (1) and its doubly 13 C labeled analogue 2, of interest for singlet fission. The hyperfine coupling constants are in excellent agreement with density functional theory calculations and establish the structures beyond doubt. Unlike the radical cation 1 •+ , the radical anion 1 •- and its parent 1 have pyramidalized nitrogen atoms and inequivalent methyl groups 15 and 16, in agreement with the calculations. The distinction is particularly clear with the labeled analogue 2 •- .

Magnetic anisotropy on the single crystal UNi4B probed by 11B NMR

NASA Astrophysics Data System (ADS)

Kishimoto, Yasuki; Matsuno, Haruki; Kotegawa, Hisashi; Tou, Hideki; Saito, Hiraku; Amitsuka, Hiroshi; Homma, Yoshiya; Nakamura, Ai; Li, Dexin; Honda, Fuminori; Aoki, Dai

2018-05-01

We have performed a susceptibility M / H and 11B NMR measurements to investigate the static magnetic anisotropy of a single crystal UNi4B. The Knight shift 11K and the hyperfine coupling constant Ahf evaluated by 11K- M / H plot show anisotropic behavior between H ∥ [ 11 2 bar 0 ] and H ∥ [ 0001 ] , reflecting the bulk susceptibility. The evaluated transferred term Atr of Ahf for H ∥ [ 11 2 bar 0 ] is much larger than the one for H ∥ [ 0001 ] . The strong hybridization in the [0001]-plane due to a itinerant 5f-electron is strongly associated with the unique magnetic structure in this compound.

Characterising molecules for fundamental physics: an accurate spectroscopic model of methyltrioxorhenium derived from new infrared and millimetre-wave measurements.

PubMed

Asselin, Pierre; Berger, Yann; Huet, Thérèse R; Margulès, Laurent; Motiyenko, Roman; Hendricks, Richard J; Tarbutt, Michael R; Tokunaga, Sean K; Darquié, Benoît

2017-02-08

Precise spectroscopic analysis of polyatomic molecules enables many striking advances in physical chemistry and fundamental physics. We use several new high-resolution spectroscopic devices to improve our understanding of the rotational and rovibrational structure of methyltrioxorhenium (MTO), the achiral parent of a family of large oxorhenium compounds that are ideal candidate species for a planned measurement of parity violation in chiral molecules. Using millimetre-wave and infrared spectroscopy in a pulsed supersonic jet, a cryogenic buffer gas cell, and room temperature absorption cells, we probe the ground state and the Re[double bond, length as m-dash]O antisymmetric and symmetric stretching excited states of both CH 3 187 ReO 3 and CH 3 185 ReO 3 isotopologues in the gas phase with unprecedented precision. By extending the rotational spectra to the 150-300 GHz range, we characterize the ground state rotational and hyperfine structure up to J = 43 and K = 41, resulting in refinements to the rotational, quartic and hyperfine parameters, and the determination of sextic parameters and a centrifugal distortion correction to the quadrupolar hyperfine constant. We obtain rovibrational data for temperatures between 6 and 300 K in the 970-1015 cm -1 range, at resolutions down to 8 MHz and accuracies of 30 MHz. We use these data to determine more precise excited-state rotational, Coriolis and quartic parameters, as well as the ground-state centrifugal distortion parameter D K of the 187 Re isotopologue. We also account for hyperfine structure in the rovibrational transitions and hence determine the upper state rhenium atom quadrupole coupling constant eQq'.

Measurement of Nitrogen Hyperfine Structure on the 53 CM (562 MHz) Butyronitrile Line

NASA Astrophysics Data System (ADS)

Dewberry, Christopher T.; Grubbs, Garry S. Grubbs, II; Raphelt, Andrew; Cooke, Stephen A.

2009-06-01

Recent improvements to our cavity-based Fourier transform radiofrequency spectrometer will be presented. Amongst other improvements use of Miteq amp, model AMF-6F-00100400-10-10P (0.1 GHz to 4 GHz, 65 dB gain minimum, 1 dB noise figure maximum) together with shielding from an improved Faraday cage have significantly helped us in this regard. Electromagnetic fields within our near-spherical cavity have been modeled and results will be presented. We have been able to easily resolve the nitrogen hyperfine structure on the ^aQ_{0,-1} transition 1_{1,0} ← 1_{1,1} located at 562 MHz. This result will be discussed.

A Simple ab initio Model for the Hydrated Electron that Matches Experiment

PubMed Central

Kumar, Anil; Walker, Jonathan A.; Bartels, David M.; Sevilla, Michael D.

2015-01-01

Since its discovery over 50 years ago, the “structure” and properties of the hydrated electron has been a subject for wonderment and also fierce debate. In the present work we seriously explore a minimal model for the aqueous electron, consisting of a small water anion cluster embedded in a polarized continuum, using several levels of ab initio calculation and basis set. The minimum energy zero “Kelvin” structure found for any 4-water (or larger) anion cluster, at any post-Hartree-Fock theory level, is very similar to a recently reported embedded-DFT-in-classical-water-MD simulation (UMJ: Uhlig, Marsalek, and Jungwirth, Journal of Physical Chemistry Letters 2012, 3, 3071-5), with four OH bonds oriented toward the maximum charge density in a small central “void”. The minimum calculation with just four water molecules does a remarkably good job of reproducing the resonance Raman properties, the radius of gyration derived from the optical spectrum, the vertical detachment energy, and the hydration free energy. For the first time we also successfully calculate the EPR g-factor and (low temperature ice) hyperfine couplings. The simple tetrahedral anion cluster model conforms very well to experiment, suggesting it does in fact represent the dominant structural motif of the hydrated electron. PMID:26275103

An electron paramagnetic resonance study on irradiated triphenylphosphinselenid single crystal

NASA Astrophysics Data System (ADS)

Aras, Erdal; Karatas, Ozgul; Meric, Yasemin; Abbass, Hind Kh; Birey, Mehmet; Kilic, Ahmet

2014-09-01

The single crystals of triphenylphosphinselenid [C18H15PSe] were produced by slow evaporation of concentrated ethyl acetate solutions. These single crystals were exposed to 60Co gamma (γ) rays with a dose speed of 0.980 kGy/h at the room temperature for 72 h. The free radical over the sample was observed using electron paramagnetic resonance (EPR)-X band spectrometer. The EPR spectra were recorded between 120 and 400 K. Furthermore, the sample irradiated was rotated in steps of 10° and analyzed for different orientations of the crystal in the magnetic field. Only one radical structure was determined on the molecule. The hyperfine constants of the sample were found to be anisotropic. The average values of these constants and value of g were calculated as following: g=2.007656, aSe=37.47 G, aP=27.44 G, aHa=17.28 G, and aHb=18.16 G.

EPR, optical and modeling of Mn(2+) doped sarcosinium oxalate monohydrate.

PubMed

Kripal, Ram; Singh, Manju

2015-01-25

Electron paramagnetic resonance (EPR) study of Mn(2+) ions doped in sarcosinium oxalate monohydrate (SOM) single crystal is done at liquid nitrogen temperature (LNT). EPR spectrum shows a bunch of five fine structure lines and further they split into six hyperfine components. Only one interstitial site was observed. With the help of EPR spectra the spin Hamiltonian parameters including zero field splitting (ZFS) parameters are evaluated. The optical absorption study at room temperature is also done in the wavelength range 195-1100 nm. From this study cubic crystal field splitting parameter, Dq=730 cm(-1) and Racah inter-electronic repulsion parameters B=792 cm(-1), C=2278 cm(-1) are determined. ZFS parameters D and E are also calculated using crystal field parameters from superposition model and microscopic spin Hamiltonian theory. The calculated ZFS parameter values are in good match with the experimental values obtained by EPR. Copyright © 2014 Elsevier B.V. All rights reserved.

Communication: theoretical study of ThO for the electron electric dipole moment search.

PubMed

Skripnikov, L V; Petrov, A N; Titov, A V

2013-12-14

An experiment to search for the electron electric dipole moment (eEDM) on the metastable H(3)Δ1 state of ThO molecule was proposed and now prepared by the ACME Collaboration [http://www.electronedm.org]. To interpret the experiment in terms of eEDM and dimensionless constant kT, P characterizing the strength of the T,P-odd pseudoscalar-scalar electron-nucleus neutral current interaction, an accurate theoretical study of an effective electric field on electron, Eeff, and a parameter of the T,P-odd pseudoscalar-scalar interaction, WT, P, in ThO is required. We report our results for Eeff (84 GV/cm) and WT, P (116 kHz) together with the hyperfine structure constant, molecule frame dipole moment, and H(3)Δ1 → X(1)Σ(+) transition energy, which can serve as a measure of reliability of the obtained Eeff and WT, P values. Besides, our results include a parity assignment and evaluation of the electric-field dependence for the magnetic g factors in the Ω-doublets of H(3)Δ1.

Pulsed EPR investigations of systems modeling molybdenum enzymes: hyperfine and quadrupole parameters of oxo-17O in [Mo 17O(SPh)4]-.

PubMed

Astashkin, Andrei V; Neese, Frank; Raitsimring, Arnold M; Cooney, J Jon A; Bultman, Eric; Enemark, John H

2005-11-30

Ka band ESEEM spectroscopy was used to determine the hyperfine (hfi) and nuclear quadrupole (nqi) interaction parameters for the oxo-17O ligand in [Mo 17O(SPh)4]-, a spectroscopic model of the oxo-Mo(V) centers of enzymes. The isotropic hfi constant of 6.5 MHz found for the oxo-17O is much smaller than the values of approximately 20-40 MHz typical for the 17O nucleus of an equatorial OH(2) ligand in molybdenum enzymes. The 17O nqi parameter (e2qQ/h = 1.45 MHz, eta approximately = 0) is the first to be obtained for an oxo group in a metal complex. The parameters of the oxo-17O ligand, as well as other magnetic resonance parameters of [Mo 17O(SPh)4]- predicted by quasi-relativistic DFT calculations, were in good agreement with those obtained in experiment. From the electronic structure of the complex revealed by DFT, it follows that the SOMO is almost entirely molybdenum d(xy) and sulfur p, while the spin density on the oxo-17O is negative, determined by spin polarization mechanisms. The results of this work will enable direct experimental identification of the oxo ligand in a variety of chemical and biological systems.

Unravelling electronic and structural requisites of triplet-triplet energy transfer by advanced electron paramagnetic resonance and density functional theory

NASA Astrophysics Data System (ADS)

Di Valentin, M.; Salvadori, E.; Barone, V.; Carbonera, D.

2013-10-01

Advanced electron paramagnetic resonance (EPR) techniques, in combination with Density Functional theory (DFT), have been applied to the comparative study of carotenoid triplet states in two major photosynthetic antenna complexes, the Peridinin-chlorophyll a-protein of dinoflagellates and the light-harvesting complex II of higher plants. Carotenoid triplet states are populated by triplet-triplet energy transfer (TTET) from chlorophyll molecules to photoprotect the system from singlet oxygen formation under light-stress conditions. The TTET process is strongly dependent on the relative arrangement and on the electronic properties of the triplet states involved. The proposed spectroscopic approach exploits the concept of spin conservation during TTET, which leads to recognisable spin polarisation effects in the time-resolved and field-swept echo-detected EPR spectra. The electron spin polarisation produced at the carotenoid acceptor site depends on the initial polarisation of the chlorophyll donor and on the relative geometrical arrangement of the donor-acceptor zero-field splitting axes. We have demonstrated that a proper analysis of the spectra in the framework of spin angular momentum conservation allows to derive the pathways of TTET and to gain insight into the structural requirements of this mechanism for those antenna complexes, whose X-ray structure is available. We have further proved that this method, developed for natural antenna complexes of known X-ray structure, can be extended to systems lacking structural information in order to derive the relative arrangement of the partners in the energy transfer process. The structural requirements for efficient TTET, obtained from time-resolved and pulse EPR, have been complemented by a detailed description of the electronic structure of the carotenoid triplet state, provided by pulse Electron-Nuclear DOuble Resonance (ENDOR) experiments. Triplet-state hyperfine couplings of the α- and β-protons of the carotenoid conjugated chain have been assigned with the aid of quantum chemical calculation. DFT predictions of the electronic structure of the carotenoid triplet state, in terms of spin density distribution, frontier orbital description and orbital excitation represent suitable building blocks toward a deeper understanding of electronic requirements for efficient TTET.

Magnetic interactions in equi-atomic rare-earth intermetallic alloys RScGe (R = Ce, Pr, Nd and Gd) studied by time differential perturbed angular correlation spectroscopy and ab initio calculations.

PubMed

Mishra, S N

2009-03-18

Applying the time differential perturbed angular correlation (TDPAC) technique we have measured electric and magnetic hyperfine fields of the (111)Cd impurity in equi-atomic rare-earth intermetallic alloys RScGe (R = Ce, Pr and Gd) showing antiferro- and ferromagnetism with unusually high ordering temperatures. The Cd nuclei occupying the Sc site show high magnetic hyperfine fields with saturation values B(hf)(0) = 21 kG, 45 kG and 189 kG in CeScGe, PrScGe and GdScGe, respectively. By comparing the results with the hyperfine field data of Cd in rare-earth metals and estimations from the RKKY model, we find evidence for the presence of additional spin density at the probe nucleus, possibly due to spin polarization of Sc d band electrons. The principal electric field gradient component V(zz) in CeScGe, PrScGe and GdScGe has been determined to be 5.3 × 10(21) V m(-2), 5.5 × 10(21) V m(-2) and 5.6 × 10(21) V m(-2), respectively. Supplementing the experimental measurements, we have carried out ab initio calculations for pure and Cd-doped RScGe compounds with R = Ce, Pr, Nd and Gd using the full potential linearized augmented plane wave (FLAPW) method based on density functional theory (DFT). From the total energies calculated with and without spin polarization we find ferrimagnetic ground states for CeScGe and PrScGe while NdScGe and GdScGe are ferromagnetic. In addition, we find a sizable magnetic moment at the Sc site, increasing from ≈0.10 μ(B) in CeScGe to ≈0.3 μ(B) in GdScGe, confirming the spin polarization of Sc d band electrons. The calculated electric field gradient and magnetic hyperfine fields of the Cd impurity closely agree with the experimental values. We believe spin polarization of Sc 3d band electrons, strongly hybridized with spin polarized 5d band electrons of the rare-earth, enables a long range Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction between RE 4f moments which in turn leads to high magnetic ordering temperatures in RScGe compounds.

Antiferromagnetic structure and electronic properties of BaCr2As2 and BaCrFeAs2

NASA Astrophysics Data System (ADS)

Filsinger, Kai A.; Schnelle, Walter; Adler, Peter; Fecher, Gerhard H.; Reehuis, Manfred; Hoser, Andreas; Hoffmann, Jens-Uwe; Werner, Peter; Greenblatt, Martha; Felser, Claudia

2017-05-01

Recent theoretical studies suggest that superconductivity may be found in doped chromium pnictides with crystal structures similar to their iron counterparts. Here, we report a comprehensive study on the magnetic arsenides BaCr2As2 and BaCrFeAs2 (space group I 4 /m m m ), which are possible mother compounds with d4 and d5 electron configurations, respectively. DFT-based calculations of the electronic structure evidence metallic antiferromagnetic ground states for both compounds. By powder neutron diffraction, we confirm for BaCr2As2 a robust ordering in the antiferromagnetic G -type structure at TN=580 K with μCr=1.9 μB . Anomalies in the lattice parameters point to magnetostructural coupling effects. In BaCrFeAs2, the Cr and Fe atoms randomly occupy the transition-metal site and G -type order is found below 265 K with μCr /Fe=1.1 μB . 57Fe Mössbauer spectroscopy demonstrates that only a small ordered moment is associated with the Fe atoms, in agreement with electronic structure calculations leading to μFe˜0 . The temperature dependence of the hyperfine field does not follow that of the total moments. Both compounds are metallic but show large enhancements of the linear specific heat. Electrical transport in BaCrFeAs2 is dominated by the atomic disorder and the partial magnetic disorder of Fe. Our results indicate that Néel-type order is unfavorable for Fe moments and thus it is destabilized with increasing Fe content.

Spin-interaction effects for ultralong-range Rydberg molecules in a magnetic field

NASA Astrophysics Data System (ADS)

Hummel, Frederic; Fey, Christian; Schmelcher, Peter

2018-04-01

We investigate the fine and spin structure of ultralong-range Rydberg molecules exposed to a homogeneous magnetic field. Each molecule consists of a 87Rb Rydberg atom the outer electron of which interacts via spin-dependent s - and p -wave scattering with a polarizable 87Rb ground-state atom. Our model includes also the hyperfine structure of the ground-state atom as well as spin-orbit couplings of the Rydberg and ground-state atom. We focus on d -Rydberg states and principal quantum numbers n in the vicinity of 40. The electronic structure and vibrational states are determined in the framework of the Born-Oppenheimer approximation for varying field strengths ranging from a few up to hundred Gauss. The results show that the interplay between the scattering interactions and the spin couplings gives rise to a large variety of molecular states in different spin configurations as well as in different spatial arrangements that can be tuned by the magnetic field. This includes relatively regularly shaped energy surfaces in a regime where the Zeeman splitting is large compared to the scattering interaction but small compared to the Rydberg fine structure, as well as more complex structures for both weaker and stronger fields. We quantify the impact of spin couplings by comparing the extended theory to a spin-independent model.

l-Tryptophan Radical Cation Electron Spin Resonance Studies: Connecting Solution-derived Hyperfine Coupling Constants with Protein Spectral Interpretations

PubMed Central

Connor, Henry D.; Sturgeon, Bradley E.; Mottley, Carolyn; Sipe, Herbert J.; Mason, Ronald P.

2009-01-01

Fast-flow electron spin resonance (ESR) spectroscopy has been used to detect a free radical formed from the reaction of l-tryptophan with Ce4+ in an acidic aqueous environment. Computer simulations of the ESR spectra from l-tryptophan and several isotopically modified forms strongly support the conclusion that the l-tryptophan radical cation has been detected by ESR for the first time. The hyperfine coupling constants (HFCs) determined from the well-resolved isotropic ESR spectra support experimental and computational efforts to understand l-tryptophan's role in protein catalysis of oxidation-reduction processes. l-tryptophan HFCs facilitated the simulation of fast-flow ESR spectra of free radicals from two related compounds, tryptamine and 3-methylindole. Analysis of these three compounds' β-methylene hydrogen HFC data along with equivalent l-tyrosine data has led to a new computational method that can distinguish between these two amino acid free radicals in proteins without dependence on isotope labeling, electron nuclear double resonance or high-field ESR. This approach also produces geometric parameters (dihedral angles for the β-methylene hydrogens) which should facilitate protein site assignment of observed l-tryptophan radicals as has been done for l-tyrosine radicals. PMID:18433127

The Submillimeter Spectrum of MnH and MnD (X7Σ+)

NASA Astrophysics Data System (ADS)

Halfen, D. T.; Ziurys, L. M.

2008-01-01

The submillimeter-wave spectrum of the MnH and MnD radicals in their 7Σ+ ground states has been measured in the laboratory using direct absorption techniques. These species were created in the gas phase by the reaction of manganese vapor, produced in a Broida-type oven, with either H2 or D2 gas in the presence of a DC discharge. The N = 0 → 1 transition of MnH near 339 GHz was recorded, which consisted of multiple hyperfine components arising from both the manganese and hydrogen nuclear spins. The N = 2 → 3 transition of MnD near 517 GHz was measured as well, but in this case only the manganese hyperfine interactions were resolved. Both data sets were analyzed with a Hund's case b Hamiltonian, and rotational, fine structure, magnetic hyperfine, and electric quadrupole constants have been determined for the two manganese species. An examination of the magnetic hyperfine constants shows that MnH is primarily an ionic species, but has more covalent character than MnF. MnH is a good candidate species for astronomical searches with Herschel, particularly toward material associated with luminous blue variable stars.

Hyperfine Quantum Beat Spectroscopy of the Cs 8p level with Pulsed Pump-Probe Technique

NASA Astrophysics Data System (ADS)

Bayram, Burcin; Popov, Oleg; Kelly, Stephen; Boyle, Patrick; Salsman, Andrew

2013-05-01

Quantum beats arising from the hyperfine interaction were measured in a three-level excitation (lambda) scheme: pump for the 6s2S1 / 2 --> 8p2P3 / 2 and stimulated emission pump (probe) for the 8p2P3 / 2 --> 5d2D5 / 2 transitions of atomic cesium. In the technique, pump laser instantaneously excites the hot atomic vapor and creates anisotropy in the 8p2P3 / 2 level, and probe laser comes after some time delay. Delaying the probe time allows us to map out the motion of the polarized atoms like a stroboscope. According to the observed evolution of the hyperfine structure dependent parameters, e.g. alignment and atomic polarization, by delaying the arrival time of the stimulated emission pump laser (SEP), precise values of the magnetic dipole and electric quadrupole coefficients are obtained with an improved precision over previous results. The usefulness of the PUMP-SEP excitation scheme for the polarization hyperfine quantum beat measurements without complications from the Doppler effect will also be discussed. The financial support of the Research Corporation under the Grant number CC7133 and MiamiUniversity, College of the Arts and Sciences are acknowledged.

Radiative transfer of HCN: interpreting observations of hyperfine anomalies

NASA Astrophysics Data System (ADS)

Mullins, A. M.; Loughnane, R. M.; Redman, M. P.; Wiles, B.; Guegan, N.; Barrett, J.; Keto, E. R.

2016-07-01

Molecules with hyperfine splitting of their rotational line spectra are useful probes of optical depth, via the relative line strengths of their hyperfine components. The hyperfine splitting is particularly advantageous in interpreting the physical conditions of the emitting gas because with a second rotational transition, both gas density and temperature can be derived. For HCN however, the relative strengths of the hyperfine lines are anomalous. They appear in ratios which can vary significantly from source to source, and are inconsistent with local thermodynamic equilibrium (LTE). This is the HCN hyperfine anomaly, and it prevents the use of simple LTE models of HCN emission to derive reliable optical depths. In this paper, we demonstrate how to model HCN hyperfine line emission, and derive accurate line ratios, spectral line shapes and optical depths. We show that by carrying out radiative transfer calculations over each hyperfine level individually, as opposed to summing them over each rotational level, the anomalous hyperfine emission emerges naturally. To do this requires not only accurate radiative rates between hyperfine states, but also accurate collisional rates. We investigate the effects of different sets of hyperfine collisional rates, derived via the proportional method and through direct recoupling calculations. Through an extensive parameter sweep over typical low-mass star-forming conditions, we show the HCN line ratios to be highly variable to optical depth. We also reproduce an observed effect whereby the red-blue asymmetry of the hyperfine lines (an infall signature) switches sense within a single rotational transition.

The 57Fe hyperfine interactions in human liver ferritin and its iron-polymaltose analogues: the heterogeneous iron core model

NASA Astrophysics Data System (ADS)

Oshtrakh, M. I.; Alenkina, I. V.; Semionkin, V. A.

2016-12-01

Human liver ferritin and its iron-polymaltose pharmaceutical analogues Ferrum Lek, Maltofer® and Ferrifol® were studied using Mössbauer spectroscopy at 295 and 90 K. The Mössbauer spectra were fitted on the basis of a new model of heterogeneous iron core structure using five quadrupole doublets. These components were related to the corresponding more or less close-packed iron core layers/regions demonstrating some variations in the 57Fe hyperfine parameters for the studied samples.

Laboratory rotational spectroscopy of cyano substituted polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

McNaughton, Don; Jahn, Michaela K.; Travers, Michael J.; Wachsmuth, Dennis; Godfrey, Peter D.; Grabow, Jens-Uwe

2018-06-01

The rotational spectra of the four cyano substituted polycyclic aromatic hydrocarbon (PAH) molecules 1-cyanonaphthalene, 2-cyanonaphthalene, 9-cyanoanthracene, and 9-cyanophenanthrene have been recorded in molecular expansions using a Stark-modulated millimetre-wave spectrometer and a Fourier transform microwave spectrometer in the centimetre-wave region. The spectra have been assigned and fitted to provide molecular constants and quadrupole hyperfine constants of sufficient accuracy to enable complete hyperfine structure line predictions for interstellar searches. The data may provide a route into detection of small PAHs in the interstellar medium.

Modified ferrite core-shell nanoparticles magneto-structural characterization

NASA Astrophysics Data System (ADS)

Klekotka, Urszula; Piotrowska, Beata; Satuła, Dariusz; Kalska-Szostko, Beata

2018-06-01

In this study, ferrite nanoparticles with core-shell structures and different chemical compositions of both the core and shell were prepared with success. Proposed nanoparticles have in the first and second series magnetite core, and the shell is composed of a mixture of ferrites with Fe3+, Fe2+ and M ions (where M = Co2+, Mn2+ or Ni2+) with a general composition of M0.5Fe2.5O4. In the third series, the composition is inverted, the core is composed of a mixture of ferrites and as a shell magnetite is placed. Morphology and structural characterization of nanoparticles were done using Transmission Electron Microscopy (TEM), X-ray diffraction (XRD), and Infrared spectroscopy (IR). While room temperature magnetic properties were measured using Mössbauer spectroscopy (MS). It is seen from Mössbauer measurements that Co always increases hyperfine magnetic field on Fe atoms at RT, while Ni and Mn have opposite influences in comparison to pure Fe ferrite, regardless of the nanoparticles structure.

Theoretical studies of the EPR parameters and local structures for Cu2+-doped cobalt ammonium phosphate hexahydrate

NASA Astrophysics Data System (ADS)

Li, Chao-Ying; Liu, Shi-Fei; Fu, Jin-Xian

2015-11-01

High-order perturbation formulas for a 3d9 ion in rhombically elongated octahedral was applied to calculate the electron paramagnetic resonance (EPR) parameters (the g factors, gi, and the hyperfine structure constants Ai, i = x, y, z) of the rhombic Cu2+ center in CoNH4PO4.6H2O. In the calculations, the required crystal-field parameters are estimated from the superposition model which enables correlation of the crystal-field parameters and hence the EPR parameters with the local structure of the rhombic Cu2+ center. Based on the calculations, the ligand octahedral (i.e. [Cu(H2O)6]2+ cluster) are found to experience the local bond length variations ΔZ (≈0.213 Å) and δr (≈0.132 Å) along axial and perpendicular directions due to the Jahn-Teller effect. Theoretical EPR parameters based on the above local structure are in good agreement with the observed values; the results are discussed.

Massively parallel implementations of coupled-cluster methods for electron spin resonance spectra. I. Isotropic hyperfine coupling tensors in large radicals

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

Verma, Prakash; Morales, Jorge A., E-mail: jorge.morales@ttu.edu; Perera, Ajith

2013-11-07

Coupled cluster (CC) methods provide highly accurate predictions of molecular properties, but their high computational cost has precluded their routine application to large systems. Fortunately, recent computational developments in the ACES III program by the Bartlett group [the OED/ERD atomic integral package, the super instruction processor, and the super instruction architecture language] permit overcoming that limitation by providing a framework for massively parallel CC implementations. In that scheme, we are further extending those parallel CC efforts to systematically predict the three main electron spin resonance (ESR) tensors (A-, g-, and D-tensors) to be reported in a series of papers. Inmore » this paper inaugurating that series, we report our new ACES III parallel capabilities that calculate isotropic hyperfine coupling constants in 38 neutral, cationic, and anionic radicals that include the {sup 11}B, {sup 17}O, {sup 9}Be, {sup 19}F, {sup 1}H, {sup 13}C, {sup 35}Cl, {sup 33}S,{sup 14}N, {sup 31}P, and {sup 67}Zn nuclei. Present parallel calculations are conducted at the Hartree-Fock (HF), second-order many-body perturbation theory [MBPT(2)], CC singles and doubles (CCSD), and CCSD with perturbative triples [CCSD(T)] levels using Roos augmented double- and triple-zeta atomic natural orbitals basis sets. HF results consistently overestimate isotropic hyperfine coupling constants. However, inclusion of electron correlation effects in the simplest way via MBPT(2) provides significant improvements in the predictions, but not without occasional failures. In contrast, CCSD results are consistently in very good agreement with experimental results. Inclusion of perturbative triples to CCSD via CCSD(T) leads to small improvements in the predictions, which might not compensate for the extra computational effort at a non-iterative N{sup 7}-scaling in CCSD(T). The importance of these accurate computations of isotropic hyperfine coupling constants to elucidate experimental ESR spectra, to interpret spin-density distributions, and to characterize and identify radical species is illustrated with our results from large organic radicals. Those include species relevant for organic chemistry, petroleum industry, and biochemistry, such as the cyclo-hexyl, 1-adamatyl, and Zn-porphycene anion radicals, inter alia.« less

Probing the Electronic Environment of Methylindoles using Internal Rotation and (14)N Nuclear Quadrupole Coupling.

PubMed

Gurusinghe, Ranil M; Tubergen, Michael J

2016-05-26

High-resolution rotational spectra were recorded in the 10.5-21.0 GHz frequency range for seven singly methylated indoles. (14)N nuclear quadrupole hyperfine structure and spectral splittings arising from tunneling along the internal rotation of the methyl group were resolved for all indole species. The nuclear quadrupole coupling constants were used to characterize the electronic environment of the nitrogen atom, and the program XIAM was used to fit the barrier to internal rotation to the measured transition frequencies. The best fit barriers were found to be 277.1(2), 374.32(4), 414.(5), 331.6(2), 126.8675(15), 121.413(4), and 426(3) cm(-1) for 1-methylindole through 7-methylindole, respectively. The fitted barriers were found to be in good agreement with barriers calculated at the ωB97XD/6-311++G(d,p) level. The complete set of experimental barriers is compared to theoretical investigations of the origins of methyl torsional barriers and confirms that the magnitude of these barriers is an overall effect of individual hyperconjugative and structural interactions of many bonding/antibonding orbitals.

Hyperfine Interactions in the Electron Paramagnetic Resonance Spectra of Point Defects in Wide-Band-Gap Semiconductors

DTIC Science & Technology

2014-09-18

compensation) during growth due to their preferred trivalent charge states. The electron paramagnetic resonance spectrum of the singly ionized chromium ...neutral nitrogen acceptor in ZnO . . . . . . . . . . . . . . . . . . 45 16 Spectrum of the singly ionized chromium acceptor in TiO2 . . . . . . . . . 49...is a single crystal of magnesium oxide that has been doped with chromium . Chromium Cr3+ substitutes for magnesium Mg2+ and creates a paramagnetic

Where's water? The many binding sites of hydantoin.

PubMed

Gruet, Sébastien; Pérez, Cristóbal; Steber, Amanda L; Schnell, Melanie

2018-02-21

Prebiotic hydantoin and its complexes with one and two water molecules are investigated using high-resolution broadband rotational spectroscopy in the 2-8 GHz frequency range. The hyperfine structure due to the nuclear quadrupole coupling of the two 14 N atoms is analysed for the monomer and the complexes. This characteristic hyperfine structure will support a definitive assignment from low frequency radioastronomy data. Experiments with H 2 18 O provide accurate experimental information on the preferred binding sites of water, which are compared with quantum-chemically calculated coordinates. In the 2-water complexes, the water molecules bind to hydantoin as a dimer instead of individually, indicating the strong water-water interactions. This information provides first insight on how hydantoin interacts with water on the molecular level.

Probing Fe-V Bonding in a C3-Symmetric Heterobimetallic Complex.

PubMed

Greer, Samuel M; McKay, Johannes; Gramigna, Kathryn M; Thomas, Christine M; Stoian, Sebastian A; Hill, Stephen

2018-04-30

Direct metal-metal bonding of two distinct first-row transition metals remains relatively unexplored compared to their second- and third-row heterobimetallic counterparts. Herein, a recently reported Fe-V triply bonded species, [V( i PrNPPh 2 ) 3 FeI] (1; Kuppuswamy, S.; Powers, T. M.; Krogman, J. P.; Bezpalko, M. W.; Foxman, B. M.; Thomas, C. M. Vanadium-iron complexes featuring metal-metal multiple bonds. Chem. Sci. 2013, 4, 3557-3565), is investigated using high-frequency electron paramagnetic resonance, field- and temperature-dependent 57 Fe nuclear gamma resonance (Mössbauer) spectroscopy, and high-field electron-electron double resonance detected nuclear magnetic resonance. From the use of this suite of physical methods, we have assessed the electronic structure of 1. These studies allow us to establish the effective g̃ tensors as well as the Fe/V electro-nuclear hyperfine interaction tensors of the spin S = 1 / 2 ground state. We have rationalized these tensors in the context of ligand field theory supported by quantum chemical calculations. This theoretical analysis suggests that the S = 1 / 2 ground state originates from a single unpaired electron predominately localized on the Fe site.

Atomic Clock Based on Opto-Electronic Oscillator

NASA Technical Reports Server (NTRS)

Maleki, Lute; Yu, Nan

2005-01-01

A proposed highly accurate clock or oscillator would be based on the concept of an opto-electronic oscillator (OEO) stabilized to an atomic transition. Opto-electronic oscillators, which have been described in a number of prior NASA Tech Briefs articles, generate signals at frequencies in the gigahertz range characterized by high spectral purity but not by longterm stability or accuracy. On the other hand, the signals generated by previously developed atomic clocks are characterized by long-term stability and accuracy but not by spectral purity. The proposed atomic clock would provide high spectral purity plus long-term stability and accuracy a combination of characteristics needed to realize advanced developments in communications and navigation. In addition, it should be possible to miniaturize the proposed atomic clock. When a laser beam is modulated by a microwave signal and applied to a photodetector, the electrical output of the photodetector includes a component at the microwave frequency. In atomic clocks of a type known as Raman clocks or coherent-population-trapping (CPT) clocks, microwave outputs are obtained from laser beams modulated, in each case, to create two sidebands that differ in frequency by the amount of a hyperfine transition in the ground state of atoms of an element in vapor form in a cell. The combination of these sidebands produces a transparency in the population of a higher electronic level that can be reached from either of the two ground-state hyperfine levels by absorption of a photon. The beam is transmitted through the vapor to a photodetector. The components of light scattered or transmitted by the atoms in the two hyperfine levels mix in the photodetector and thereby give rise to a signal at the hyperfine- transition frequency. The proposed atomic clock would include an OEO and a rubidium- or cesium- vapor cell operating in the CPT/Raman regime (see figure). In the OEO portion of this atomic clock, as in a typical prior OEO, a laser beam would pass through an electro-optical modulator, the modulated beam would be fed into a fiber-optic delay line, and the delayed beam would be fed to a photodetector. The electrical output of the photodetector would be detected, amplified, filtered, and fed back to the microwave input port of the modulator. The laser would be chosen to have the same wavelength as that of the pertinent ground-state/higher-state transition of the atoms in the vapor. The modulator/ filter combination would be designed to operate at the microwave frequency of the hyperfine transition. Part of the laser beam would be tapped from the fiberoptic loop of the OEO and introduced into the vapor cell. After passing through the cell, this portion of the beam would be detected differentially with a tapped portion of the fiber-optically-delayed beam. The electrical output of the photodetector would be amplified and filtered in a loop that would control a DC bias applied to the modulator. In this manner, the long-term stability and accuracy of the atomic transition would be transferred to the OEO.

Research investigation directed toward extending the useful range of the electromagnetic spectrum

NASA Technical Reports Server (NTRS)

Hartmann, S. R.

1971-01-01

The lifetimes and fine structure of He(-) were studied using time-of-flight techniques and quenching by a static axial magnetic field. Using level-crossing spectroscopy the hyperfine constants A and B and the lifetime of the 3 2P3/2 state of Li-7 were measured. Polarization of the Ru 7S level was created as a first step in determining the hyperfine structure of the alkali excited S state. The parametric interaction between light and microwaves in optically pumped Rb-87 vapor were investigated. Measurements and analyses of transitions in formaldehyde and its isotopic species and in the lowest two excited vibrational states of H2CO were also made, as well as of transitions in furan, pyrrole, formic acid, and cyanoacetylene. The Hanle effect was studied in the NO molecule, and RF oscillators were developed with flat, wideband output to observe excited state hyperfine transitions at zero field. Data was generated on the time-dependent behavior of photon echoes in ruby. Stimulated Raman scattering was studied in atomic Tl vapor. A Q switched, temperature-tuned ruby laser was developed which operates between 6934 and 6938 A. The frequency shift due to resonant interaction between identical radiating atoms was calculated.

Electron paramagnetic resonance of gamma-irradiated single crystals of 3-nitroacetanilide

NASA Astrophysics Data System (ADS)

Aşik, Biray

2008-06-01

The electron paramagnetic resonance of single crystals of 3-nitroacetanilide has been observed and analyzed for different orientations of the crystal in the magnetic field, after being damaged at 300 K by γ-irradiation. The crystals have been investigated between 123 and 300 K. The spectra were found to be temperature independent. The irradiation of 3-nitroacetanilide by γ-rays produces radicals at the nitrogen atoms in the molecule. The principal values of the hyperfine coupling tensor of the unpaired electron and the principal values of the g-tensor were determined.

Electronuclear paths in the nuclear conversion of molecular hydrogen in silicon

NASA Astrophysics Data System (ADS)

Ilisca, Ernest; Ghiglieno, Filippo

2017-01-01

The ortho-para conversion of hydrogen molecules oscillating inside tetrahedral cages of silicon compounds relies on the interaction of the nuclear protons with the silicon electrons. At each collision against the cage hard walls, the electron repulsion changes the molecular rotation while projecting a valence electron in the antibonding molecular state dressed by a group of conduction ones. That «bridge» facilitates the hyperfine contact of the electrons with the protons. At room temperature, the angular momentum transfer is enhanced by electron fluctuations that overcome the silicon gap and accelerate the nuclear rates by more than one order of magnitude.

Local magnetic moment formation at 119Sn Mössbauer impurity in RFe2 ( R=rare-earth metals) Laves phases compounds

NASA Astrophysics Data System (ADS)

de Oliveira, A. L.; de Oliveira, N. A.; Troper, A.

2010-05-01

The purpose of the present work is to theoretically study the local magnetic moment formation and the systematics of the magnetic hyperfine fields at a non-magnetic s-p Mössbauer 119Sn impurity diluted on R sites ( R=rare-earth metals) of the cubic Laves phases intermetallic compounds RFe2. One considers that the magnetic hyperfine field has two contributions (i) the contribution from R ions, calculated via an extended Daniel-Friedel [J. Phys. Chem. Solids 24 (1963) 1601] model and (ii) the contribution from the induced magnetic moments arising from the Fe neighboring sites. We have in this case a two-center Blandin-Campbell-like [Phys. Rev. Lett. 31 (1973) 51; J. Magn. Magn. Mater. 1 (1975) 1] problem, where a magnetic 3d-element located at a distance from the 119Sn impurity gives an extra magnetization to a polarized electron gas which is strongly charge perturbed at the 119Sn impurity site. We also include in the model, the nearest-neighbor perturbation due to the translational invariance breaking introduced by the impurity. Our self-consistent total magnetic hyperfine field calculations are in a very good agreement with recent experimental data.

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.

Lande gJ factors for even-parity electronic levels in the holmium atom

NASA Astrophysics Data System (ADS)

Stefanska, D.; Werbowy, S.; Krzykowski, A.; Furmann, B.

2018-05-01

In this work the hyperfine structure of the Zeeman splitting for 18 even-parity levels in the holmium atom was investigated. The experimental method applied was laser induced fluorescence in a hollow cathode discharge lamp. 20 spectral lines were investigated involving odd-parity levels from the ground multiplet, for which Lande gJ factors are known with high precision, as the lower levels; this greatly facilitated the evaluation of gJ factors for the upper levels. The gJ values for the even-parity levels considered are reported for the first time. They proved to compare fairly well with the values obtained recently in a semi-empirical analysis for the even-parity level system of Ho I.

Identification of the Ga interstitial in Al(x)Ga(1-x)As by optically detected magnetic resonance

NASA Technical Reports Server (NTRS)

Kennedy, T. A.; Spencer, M. G.

1986-01-01

A new optically detected magnetic resonance spectrum in Al(x)Ga(1-x)As is reported and assigned to native Ga interstitials. Luminescence-quenching signals were observed over the energy region from 0.75 to 1.1 eV. The optically detected magnetic resonance is nearly isotropic, with spin-Hamiltonian parameters g = 2.025 + or - 0.006, central hyperfine splitting A(Ga-69) = 0.050 + or - 0.001/cm, and A(Ga-71) = 0.064 + or - 0.001/cm for H near the 001 line. The strong hyperfine coupling denotes an electronic state of A1 symmetry, which current theories predict for the Ga interstitial but not the Ga antisite. The slight anisotropy probably indicates that the Ga(i) is paired with a second, unknown defect.

Effects of thermal annealing on the radiation produced electron paramagnetic resonance spectra of bovine and equine tooth enamel: Fossil and modern

NASA Astrophysics Data System (ADS)

Weeks, Robert A.; Bogard, James S.; Elam, J. Michael; Weinand, Daniel C.; Kramer, Andrew

2003-06-01

The concentration of stable radiation-induced paramagnetic states in fossil teeth can be used as a measure of sample age. Temperature excursions >100 °C, however, can cause the paramagnetic state clock to differ from the actual postmortem time. We have heated irradiated enamel from both fossilized bovid and modern equine (MEQ) teeth for 30 min in 50 °C increments from 100 to 300 °C, measuring the electron paramagnetic resonance (EPR) spectrum after each anneal, to investigate such effects. Samples were irradiated again after the last anneal, with doses of 300-1200 Gy from 60Co photons, and measured. Two unirradiated MEQ samples were also annealed for 30 min at 300 °C, one in an evacuated EPR tube and the other in a tube open to the atmosphere, and subsequently irradiated. The data showed that hyperfine components attributed to the alanine radical were not detected in the irradiated MEQ sample until after the anneals. The spectrum of the MEQ sample heated in air and then irradiated was similar to that of the heat treated fossil sample. We conclude that the hyperfine components are due to sample heating to temperatures/times >100 °C/30 min and that similarities between fossil and MEQ spectra after the 300 °C/30 min MEQ anneal are also due to sample heating. We conclude that the presence of the hyperfine components in spectra of fossil tooth enamel indicate that such thermal events occurred either at the time of death, or during the postmortem history.

ENDOR with band-selective shaped inversion pulses

NASA Astrophysics Data System (ADS)

Tait, Claudia E.; Stoll, Stefan

2017-04-01

Electron Nuclear DOuble Resonance (ENDOR) is based on the measurement of nuclear transition frequencies through detection of changes in the polarization of electron transitions. In Davies ENDOR, the initial polarization is generated by a selective microwave inversion pulse. The rectangular inversion pulses typically used are characterized by a relatively low selectivity, with full inversion achieved only for a limited number of spin packets with small resonance offsets. With the introduction of pulse shaping to EPR, the rectangular inversion pulses can be replaced with shaped pulses with increased selectivity. Band-selective inversion pulses are characterized by almost rectangular inversion profiles, leading to full inversion for spin packets with resonance offsets within the pulse excitation bandwidth and leaving spin packets outside the excitation bandwidth largely unaffected. Here, we explore the consequences of using different band-selective amplitude-modulated pulses designed for NMR as the inversion pulse in ENDOR. We find an increased sensitivity for small hyperfine couplings compared to rectangular pulses of the same bandwidth. In echo-detected Davies-type ENDOR, finite Fourier series inversion pulses combine the advantages of increased absolute ENDOR sensitivity of short rectangular inversion pulses and increased sensitivity for small hyperfine couplings of long rectangular inversion pulses. The use of pulses with an almost rectangular frequency-domain profile also allows for increased control of the hyperfine contrast selectivity. At X-band, acquisition of echo transients as a function of radiofrequency and appropriate selection of integration windows during data processing allows efficient separation of contributions from weakly and strongly coupled nuclei in overlapping ENDOR spectra within a single experiment.

Two tyrosyl radicals stabilize high oxidation states in cytochrome c oxidase for efficient energy conservation and proton translocation

NASA Astrophysics Data System (ADS)

Rousseau, Denis

2012-02-01

The reaction of hydrogen peroxide (H2O2) with oxidized bovine cytochrome c oxidase (bCcO) was studied by electron paramagnetic resonance (EPR) to determine the properties of radical intermediates. Two distinct radicals with widths of 12 and 46 G are directly observed by X-band CW-EPR in the reaction of bCcO with H2O2 at pH 6 and pH 8. High-frequency EPR (D-band) provides assignments to tyrosine for both radicals based on well-resolved g-tensors. The 46 G wide radical has extensive hyperfine structure and can be fit with parameters consistent with Y129. However, the 12 G wide radical has minimal hyperfine structure and can be fit using parameters unique to the post-translationally modified Y244 in CcO. The results are supported by mixed quantum mechanics and molecular mechanics calculations. This study reports spectroscopic evidence of a radical formed on the modified tyrosine in CcO and resolves the much debated controversy of whether the wide radical seen at low pH in the bovine system is a tyrosine or tryptophan. A model is presented showing how radical formation and migration may play an essential role in proton translocation. This work was done in collaboration with Michelle A. Yu, Tsuyoshi Egawa, Syun-Ru Yeh and Gary J. Gerfen from Albert Einstein College of Medicine; Kyoko Shinzawa-Itoh and Shinya Yoshikawa from the University of Hyogo; and Victor Guallar from the Barcelona Supercomputing Center.

Precision Muonium Spectroscopy

NASA Astrophysics Data System (ADS)

Jungmann, Klaus P.

2016-09-01

The muonium atom is the purely leptonic bound state of a positive muon and an electron. It has a lifetime of 2.2 µs. The absence of any known internal structure provides for precision experiments to test fundamental physics theories and to determine accurate values of fundamental constants. In particular ground state hyperfine structure transitions can be measured by microwave spectroscopy to deliver the muon magnetic moment. The frequency of the 1s-2s transition in the hydrogen-like atom can be determined with laser spectroscopy to obtain the muon mass. With such measurements fundamental physical interactions, in particular quantum electrodynamics, can also be tested at highest precision. The results are important input parameters for experiments on the muon magnetic anomaly. The simplicity of the atom enables further precise experiments, such as a search for muonium-antimuonium conversion for testing charged lepton number conservation and searches for possible antigravity of muons and dark matter.

Conformational differences between the methoxy groups of QA and QB site ubisemiquinones in bacterial reaction centers: a key role for methoxy group orientation in modulating ubiquinone redox potential.

PubMed

Taguchi, Alexander T; O'Malley, Patrick J; Wraight, Colin A; Dikanov, Sergei A

2013-07-09

Ubiquinone is an almost universal, membrane-associated redox mediator. Its ability to accept either one or two electrons allows it to function in critical roles in biological electron transport. The redox properties of ubiquinone in vivo are determined by its environment in the binding sites of proteins and by the dihedral angle of each methoxy group relative to the ring plane. This is an attribute unique to ubiquinone among natural quinones and could account for its widespread function with many different redox complexes. In this work, we use the photosynthetic reaction center as a model system for understanding the role of methoxy conformations in determining the redox potential of the ubiquinone/semiquinone couple. Despite the abundance of X-ray crystal structures for the reaction center, quinone site resolution has thus far been too low to provide a reliable measure of the methoxy dihedral angles of the primary and secondary quinones, QA and QB. We performed 2D ESEEM (HYSCORE) on isolated reaction centers with ubiquinones (13)C-labeled at the headgroup methyl and methoxy substituents, and have measured the (13)C isotropic and anisotropic components of the hyperfine tensors. Hyperfine couplings were compared to those derived by DFT calculations as a function of methoxy torsional angle allowing estimation of the methoxy dihedral angles for the semiquinones in the QA and QB sites. Based on this analysis, the orientation of the 2-methoxy groups are distinct in the two sites, with QB more out of plane by 20-25°. This corresponds to an ≈50 meV larger electron affinity for the QB quinone, indicating a substantial contribution to the experimental difference in redox potentials (60-75 mV) of the two quinones. The methods developed here can be readily extended to ubiquinone-binding sites in other protein complexes.

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.

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.

Molecules in high spin states: The millimeter and submillimeter spectrum of the MnS radical (X 6Sigma+)

NASA Astrophysics Data System (ADS)

Thompsen, J. M.; Brewster, M. A.; Ziurys, L. M.

2002-06-01

The pure rotational spectrum of MnS (v=0) in its X 6Sigma+ ground state has been recorded using millimeter and submillimeter direct absorption techniques in the range 160-502 GHz. MnS was synthesized in the gas phase by the reaction of manganese vapor and CS2 in a high-temperature Broida-type oven. Fourteen rotational transitions for this radical were measured, each consisting of six fine-structure components. In the lower rotational lines, hyperfine structure, arising from the 55Mn nuclear spin of 5/2, was also resolved in each spin component. These data were analyzed using a case (b) Hamiltonian, and rotational, fine structure, and hyperfine parameters determined for MnS. In the analysis, the third-order correction to the spin-rotation interaction, gammaS, and the fourth-order spin-spin coupling term, theta, were found necessary for an acceptable fit. The hyperfine constants determined suggest that MnS is more covalent than MnO, but more ionic than MnH. There additionally appears to be considerable sdsigma hybridization in molecular orbital formation for this molecule. Bond lengths of the 3d transition-metal sulfides were compared as well, and those of MnS, CuS, and TiS do not follow the trend of their oxide analogs. This result indicates that there are significant bonding differences between transition-metal sulfides and transition-metal oxides.

Rotational spectroscopic study of carbonyl sulfide solvated with hydrogen molecules.

PubMed

Michaud, Julie M; Jäger, Wolfgang

2008-10-14

Rotational spectra of small-sized (H(2))(N)-OCS clusters with N = 2-7 were measured using a pulsed-jet Fourier transform microwave spectrometer. These include spectra of pure (para-H(2))(N)-OCS clusters, pure (ortho-H(2))(N)-OCS clusters, and mixed ortho-H(2) and para-H(2) containing clusters. The rotational lines of ortho-H(2) molecules containing clusters show proton spin-proton spin hyperfine structure, and the pattern evolves as the number of ortho-H(2) molecules in the cluster increases. Various isotopologues of the clusters were investigated, including those with O(13)CS, OC(33)S, OC(34)S, and O(13)C(34)S. Nuclear quadrupole hyperfine structures of rotational transitions were observed for (33)S (nuclear spin quantum number I = 3/2) containing isotopologues. The (33)S nuclear quadrupole coupling constants are compared to the corresponding constant of the OCS monomer and those of the He(N)-OCS clusters. The assignment of the number of solvating hydrogen molecules N is supported by the analyses of the proton spin-proton spin hyperfine structures of the mixed clusters, the dependence of line intensities on sample conditions (pressure and concentrations), and the agreement of the (para-H(2))(N)-OCS and (ortho-H(2))(N)-OCS rotational constants with those from a previous infrared study [J. Tang and A. R. W. McKellar, J. Chem. Phys. 121, 3087 (2004)].

Structure and magnetic behaviors of melt-spun SmFeSiB ribbons and their nitrides

NASA Astrophysics Data System (ADS)

Luo, Y.; Zhang, K.; Li, K. S.; Yu, D. B.; Ling, J. J.; Men, K.; Dou, Q. Y.; Yan, W. L.; Xie, J. J.; Yang, Y. F.

2016-05-01

SmFe9.3+xSi0.2B0.1 (x=0, 0.5, 1.0) ribbons and their nitrides were prepared by melt-spinning, followed by annealing and subsequent nitriding. The structure and magnetic properties have been investigated by means of powder X-ray diffraction, vibrating sample magnetometer and Mossbauer spectroscopy. Rietveld analysis shows that the augment of Fe content gives rise to an increase of the c/a ratio and cell volume. The increasing amount of Fe atoms occupying the 2e sites results in the change of initial structure. It is indicated that the isomer shift of 3g and 6l atom remains quasi-constant while the 2e atom shows a noticeable increase with the increase of iron content, which further conforms the preferential occupation of excessive Fe atoms at this site. Consistent with Tc, the mean hyperfine field 〈Bhf〉 has the highest value of 25.7 T when x=0.5. The hyperfine fields at different Fe sites follow the order H2e>H3g>H6l. The highest curie temperature of 477.68 K and the hyperfine field of 25.7 T in the as-quenched ribbons were obtained when x=0.5. Meanwhile, the highest magnetic properties of Hcj=4.31 kOe, (BH)m=3.5 MGOe in the nitride powders were found.

Magnetoelectroluminescence of organic heterostructures: Analytical theory and spectrally resolved measurements

DOE PAGES

Liu, Feilong; Kelley, Megan R.; Crooker, Scott A.; ...

2014-12-22

The effect of a magnetic field on the electroluminescence of organic light emitting devices originates from the hyperfine interaction between the electron/hole polarons and the hydrogen nuclei of the host molecules. In this paper, we present an analytical theory of magnetoelectroluminescence for organic semiconductors. To be specific, we focus on bilayer heterostructure devices. In the case we are considering, light generation at the interface of the donor and acceptor layers results from the formation and recombination of exciplexes. The spin physics is described by a stochastic Liouville equation for the electron/hole spin density matrix. By finding the steady-state analytical solutionmore » using Bloch-Wangsness-Redfield theory, we explore how the singlet/triplet exciplex ratio is affected by the hyperfine interaction strength and by the external magnetic field. In order to validate the theory, spectrally resolved electroluminescence experiments on BPhen/m-MTDATA devices are analyzed. With increasing emission wavelength, the width of the magnetic field modulation curve of the electroluminescence increases while its depth decreases. Furthermore, these observations are consistent with the model.« less

14N Quadrupole Coupling in the Microwave Spectra of N-Vinylformamide

NASA Astrophysics Data System (ADS)

Kannengießer, Raphaela; Stahl, Wolfgang; Nguyen, Ha Vinh Lam; Bailey, William C.

2016-06-01

The microwave spectra of two conformers, trans and cis, of the title compound were recorded using two molecular beam Fourier transform microwave spectrometers operating in the frequency range 2 GHz to 40 GHz, and aimed at analysis of their 14N quadrupole hyperfine structures. Rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling constants (NQCCs) χaa and χbb - χcc, were all determined with very high accuracy. Two fits including 176 and 117 hyperfine transitions were performed for the trans and cis conformers, respectively. Standard deviations of both fits are close to the measurement accuracy of 2 kHz. The NQCCs of the two conformers are almost exactly the same, and are compared with values found for other saturated and unsaturated formamides. Complementary quantum chemical calculations - MP2/6-311++G(d,p) rotational constants, MP2/cc-pVTZ centrifugal distortion constants, and B3PW91/6-311+G(d,p)//MP2/6-311++G(d,p) nuclear quadrupole coupling constants - give spectroscopic parameters in excellent agreement with the experimental parameters. B3PW91/6-311+G(d,p) calculated electric field gradients, in conjunction with eQ/h = 4.599(12) MHz/a.u., yields more reliable NQCCs for formamides possessing conjugated π-electron systems than does the B3PW91/6-311+G(df,pd) model recommended in Ref., whereas this latter performs better for aliphatic formamides. We conclude from this that f-polarization functions on heavy atoms hinder rather than help with modeling of conjugated π-electron systems. W. C. Bailey, Chem. Phys., 2000, 252, 57 W. C. Bailey, Calculation of Nuclear Quadrupole Coupling Constants in Gaseous State Molecules, http://nqcc.wcbailey.net/index.html.

Hyperfine interaction and its effects on spin dynamics in organic solids

NASA Astrophysics Data System (ADS)

Yu, Z. G.; Ding, Feizhi; Wang, Haobin

2013-05-01

Hyperfine interaction (HFI) and spin-orbit coupling are two major sources that affect electron spin dynamics. Here we present a systematic study of the HFI and its role in organic spintronic applications. For electron spin dynamics in disordered π-conjugated organics, the HFI can be characterized by an effective magnetic field whose modular square is a weighted sum of contact and dipolar contributions. We determine the effective HFI fields of some common π-conjugated organics studied in the literature via first-principles calculations. Most of them are found to be less than 2 mT. While the H atoms are the major source of the HFI in organics containing only the C and H atoms, many organics contain other nuclear spins, such as Al and N in tris-(8-hydroxyquinoline) aluminum, that contribute to the total HFI. Consequently, the deuteration effect on the HFI in the latter may be much weaker than in the former. The HFI gives rise to multiple resonance peaks in electron spin resonance. In disordered organic solids, these individual resonances are unresolved, leading to a broad peak whose width is proportional to the effective HFI field. As electrons hop among adjacent organic molecules, they experience a randomly varying local HFI field, inducing electron spin relaxation and diffusion. This is analyzed rigorously based on master equations. Electron spin relaxation undergoes a crossover along the ratio between the electron hopping rate η¯ and the Larmor frequency Ω of the HFI field. The spin relaxation rate increases (decreases) with η¯ when η¯≪Ω (η¯≫Ω). A coherent beating of electron spin at Ω is possible when the external field is small compared to the HFI. In this regime, the magnetic field is found to enhance the spin relaxation.

Spectroscopy of the 1/2 2S → 3/2 2P transition in Yb ii: Isotope shifts, hyperfine splitting, and branching ratios

NASA Astrophysics Data System (ADS)

Feldker, T.; Fürst, H.; Ewald, N. V.; Joger, J.; Gerritsma, R.

2018-03-01

We report on spectroscopic results on the 1/2 2S → 3/2 2P transition in single trapped Yb+ ions. We measure the isotope shifts for all stable Yb+ isotopes except +173Yb, as well as the hyperfine splitting of the 3/2 2P state in +171Yb. Our results are in agreement with previous measurements but are a factor of 5-9 more precise. For the hyperfine constant A (3/2 2P)=875.4 (10 )MHz our results also agree with previous measurements but deviate significantly from theoretical predictions. We present experimental results on the branching ratios for the decay of the 3/2 2P state. We find branching fractions for the decay to the 3/2 2D state and 5/2 2D state of 0.17(1)% and 1.08(5)%, respectively, in rough agreement with theoretical predictions. Furthermore, we measured the isotope shifts of the 7/2 2F →1D[5/2 ] 5 /2 transition and determine the hyperfine structure constant for the 1D[5/2 ] 5 /2 state in +171Yb to be A (1D[5/2 ] 5 /2)=-107 (6 ) MHz .

Investigation of 3C-SiC/SiO2 interfacial point defects from ab initio g-tensor calculations and electron paramagnetic resonance measurements

NASA Astrophysics Data System (ADS)

Nugraha, T. A.; Rohrmueller, M.; Gerstmann, U.; Greulich-Weber, S.; Stellhorn, A.; Cantin, J. L.; von Bardeleben, J.; Schmidt, W. G.; Wippermann, S.

SiC is widely used in high-power, high-frequency electronic devices. Recently, it has also been employed as a building block in nanocomposites used as light absorbers in solar energy conversion devices. Analogous to Si, SiC features SiO2 as native oxide that can be used for passivation and insulating layers. However, a significant number of defect states are reported to form at SiC/SiO2 interfaces, limiting mobility and increasing recombination of free charge carriers. We investigated the growth of oxide on different 3C-SiC surfaces from first principles. Carbon antisite Csi defects are found to be strongly stabilized in particular at the interface, because carbon changes its hybridization from sp3 in the SiC-bulk to sp2 at the interface, creating a dangling bond inside a porous region of the SiO2 passivating layer. Combining ab initio g-tensor calculations and electron paramagnetic resonance (EPR) measurements, we show that Csi defects explain the measured EPR signatures, while the hyperfine structure allows to obtain local structural information of the oxide layer. Financial support from BMBF NanoMatFutur Grant 13N12972 and DFG priority program SPP-1601 is gratefully acknowledged.

133Cs-NMR Study on the Ground State of the Equilateral Triangular Spin Tube CsCrF4

NASA Astrophysics Data System (ADS)

Matsui, K.; Goto, T.; Manaka, H.; Miura, Y.

2018-03-01

We have investigated the hyperfine coupling between Cs and Cr on the S = 3/2 equilateral triangular spin tube CsCrF4, utilizing 133Cs-NMR. At paramagnetic state above 80 K, we have obtained spectra containing a single peak, which reflects the single crystallographic Cs site. From the temperature dependence of the peak shift and peak width, we evaluated effective values of the isotropic and the anisotropic part of hyperfine coupling. The latter was compared with the calculated dipole contribution. Using obtained parameters with assumed spin structure, we tried to reproduce the broadened spectrum in the ordered state at 2.0 K. The preliminary analysis shows the 120-degree structure does not accord with the observed spectra at the ordered state.

Mössbauer spectra of iron (III) sulfide particles

NASA Astrophysics Data System (ADS)

Kubono, I.; Nishida, N.; Kobayashi, Y.; Yamada, Y.

2017-11-01

Trivalent iron sulfide (Fe2 S 3) particles were synthesized using a modified polyol method. These particles exhibited a needle-like shape (diameter = 10-50 nm, length = 350-1000 nm) and generated a clear XRD pattern. Mössbauer spectra of the product showed a paramagnetic doublet at room temperature and distributed hyperfine magnetic splitting at low temperature. The Curie temperature of this material was determined to be approximately 60 K. The data suggest that the Fe2 S 3 had a structure similar to that of maghemite ( γ-Fe2 O 3) with a lattice constant of a = 10.6 Å. The XRD pattern calculated from this structure was in agreement with the experimental pattern and the calculated hyperfine magnetic field was also equivalent to that observed in the experimental Mössbauer spectrum.

Synthesis and atomic scale characterization of Er2O3 nanoparticles: enhancement of magnetic properties and changes in the local structure

NASA Astrophysics Data System (ADS)

Corrêa, Eduardo L.; Bosch-Santos, Brianna; Freitas, Rafael S.; Potiens, Maria da Penha A.; Saiki, Mitiko; Carbonari, Artur W.

2018-05-01

In the investigation reported in this paper a modified thermal decomposition method was developed to produce very small Er2O3 nanoparticles (NPs). Particles structure, shape and size were characterized by x-ray diffraction and transmission electron microscopy which showed that the synthesis by thermal decomposition under O2 atmosphere produced very small and monodisperse NPs, allowing the investigation of finite-size and surface effects. Results of magnetization measurements showed that the smallest particles present the highest values of susceptibility that decrease as particle size increases. Specific heat measurements indicate that the sample with the smallest NPs (diameter ∼5 nm) has a Néel temperature of 0.54 K. The local structure of particles was investigated by measurements of hyperfine interactions with perturbed angular correlation spectroscopy using 111Cd as probe nuclei replacing the cationic sites. Results showed that the relative population of sites 8b increases in both the core and surface layer of particles.

Structures and reaction pathways of the molybdenum centres of sulfite-oxidizing enzymes by pulsed EPR spectroscopy.

PubMed

Enemark, John H; Astashkin, Andrei V; Raitsimring, Arnold M

2008-12-01

SOEs (sulfite-oxidizing enzymes) are physiologically vital and occur in all forms of life. During the catalytic cycle, the five-co-ordinate square pyramidal oxo-molybdenum active site passes through the Mo(V) state, and intimate details of the structure can be obtained from variable frequency pulsed EPR spectroscopy through the hyperfine and nuclear quadrupole interactions of nearby magnetic nuclei. By employing variable spectrometer operational frequencies, it is possible to optimize the measurement conditions for difficult quadrupolar nuclei of interest (e.g. (17)O, (33)S, (35)Cl and (37)Cl) and to simplify the interpretation of the spectra. Isotopically labelled model Mo(V) compounds provide further insight into the electronic and geometric structures and chemical reactions of the enzymes. Recently, blocked forms of SOEs having co-ordinated sulfate, the reaction product, were detected using (33)S (I=3/2) labelling. This blocking of product release is a possible contributor to fatal human sulfite oxidase deficiency in young children.

Synthesis and atomic scale characterization of Er2O3 nanoparticles: enhancement of magnetic properties and changes in the local structure.

PubMed

Corrêa, Eduardo L; Bosch-Santos, Brianna; Freitas, Rafael S; da Penha A Potiens, Maria; Saiki, Mitiko; Carbonari, Artur W

2018-05-18

In the investigation reported in this paper a modified thermal decomposition method was developed to produce very small Er 2 O 3 nanoparticles (NPs). Particles structure, shape and size were characterized by x-ray diffraction and transmission electron microscopy which showed that the synthesis by thermal decomposition under O 2 atmosphere produced very small and monodisperse NPs, allowing the investigation of finite-size and surface effects. Results of magnetization measurements showed that the smallest particles present the highest values of susceptibility that decrease as particle size increases. Specific heat measurements indicate that the sample with the smallest NPs (diameter ∼5 nm) has a Néel temperature of 0.54 K. The local structure of particles was investigated by measurements of hyperfine interactions with perturbed angular correlation spectroscopy using 111 Cd as probe nuclei replacing the cationic sites. Results showed that the relative population of sites 8b increases in both the core and surface layer of particles.

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-assisted spin diffusion process on variations of the relevant parameters. In particular, the effect of the spin lattice relaxation times on the polarization buildup times and the resulting end polarization are discussed, and the quenching of the polarizations by the hyperfine interaction is demonstrated.

Characterization of methanol as a magnetic field tracer in star-forming regions

NASA Astrophysics Data System (ADS)

Lankhaar, Boy; Vlemmings, Wouter; Surcis, Gabriele; van Langevelde, Huib Jan; Groenenboom, Gerrit C.; van der Avoird, Ad

2018-02-01

Magnetic fields play an important role during star formation1. Direct magnetic field strength observations have proven particularly challenging in the extremely dynamic protostellar phase2-4. Because of their occurrence in the densest parts of star-forming regions, masers, through polarization observations, are the main source of magnetic field strength and morphology measurements around protostars2. Of all maser species, methanol is one of the strongest and most abundant tracers of gas around high-mass protostellar disks and in outflows. However, as experimental determination of the magnetic characteristics of methanol has remained largely unsuccessful5, a robust magnetic field strength analysis of these regions could hitherto not be performed. Here, we report a quantitative theoretical model of the magnetic properties of methanol, including the complicated hyperfine structure that results from its internal rotation6. We show that the large range in values of the Landé g factors of the hyperfine components of each maser line lead to conclusions that differ substantially from the current interpretation based on a single effective g factor. These conclusions are more consistent with other observations7,8 and confirm the presence of dynamically important magnetic fields around protostars. Additionally, our calculations show that (nonlinear) Zeeman effects must be taken into account to further enhance the accuracy of cosmological electron-to-proton mass ratio determinations using methanol9-12.

Electron spin resonance of (CO 2 H)CH 2 CH 2 CH(CO 2 H) in irradiated glutaric acid

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

Horsfield, A.; Morton, J. R.; Whiffen, D. H.

It is concluded from electron spin resonance spectra that the radical (CO 2 H)CH 2 CH 2 CH(CO 2 H) remains trapped in a glutaric acid crystal after gamma -irradiation. This radical is found in two different conformations. Approximate hyperfine coupling constants are given for each, although exact interpretation is hindered by the overlapping of spectra. Reasons for the formation of the two forms of the radical are discussed.

Rabi oscillation and electron-spin-echo envelope modulation of the photoexcited triplet spin system in silicon

NASA Astrophysics Data System (ADS)

Akhtar, Waseem; Sekiguchi, Takeharu; Itahashi, Tatsumasa; Filidou, Vasileia; Morton, John J. L.; Vlasenko, Leonid; Itoh, Kohei M.

2012-09-01

We report on a pulsed electron paramagnetic resonance (EPR) study of the photoexcited triplet state (S=1) of oxygen-vacancy centers in silicon. Rabi oscillations between the triplet sublevels are observed using coherent manipulation with a resonant microwave pulse. The Hahn echo and stimulated echo decay profiles are superimposed with strong modulations known as electron-spin-echo envelope modulation (ESEEM). The ESEEM spectra reveal a weak but anisotropic hyperfine coupling between the triplet electron spin and a 29Si nuclear spin (I=1/2) residing at a nearby lattice site, that cannot be resolved in conventional field-swept EPR spectra.

57Fe Mössbauer study of unusual magnetic structure of multiferroic 3R-AgFeO2

NASA Astrophysics Data System (ADS)

Sobolev, A.; Rusakov, V.; Moskvin, A.; Gapochka, A.; Belik, A.; Glazkova, I.; Akulenko, A.; Demazeau, G.; Presniakov, I.

2017-07-01

We report new results of a 57Fe Mössbauer study of hyperfine magnetic interactions in the layered multiferroic 3R-AgFeO2 demonstrating two magnetic phase transitions at T N1 and T N2. The asymptotic value β *  ≈  0.34 for the critical exponent obtained from the temperature dependence of the hyperfine field H hf(T) at 57Fe the nuclei below T N1  ≈  14 K indicates that 3R-AgFeO2 shows quasi-3D critical behavior. The spectra just above T N1 (T N1  <  T  <  T  *  ≈  41 K) demonstrate a relaxation behavior due to critical spin fluctuations which indicates the occurrence of short-range correlations. At the intermediate temperature range, T N2  <  T  <  T N1, the 57Fe Mössbauer spectra are described in terms of collinear spin-density-waves (SDW) with the inclusion of many high-order harmonics, indicating that the real magnetic structure of the ferrite appears to be more complicated than a pure sinusoidally modulated SDW. Below T  <  T N2  ≈  9 K, the hyperfine field H hf reveals a large spatial anisotropy (ΔH anis  ≈  30 kOe) which is related with a local intra-cluster (FeO6) spin-dipole term that implies a conventional contribution of the polarized oxygen ions. We proposed a simple two-parametric formula to describe the dependence of H anis on the distortions of the (FeO6) clusters. Analysis of different mechanisms of spin and hyperfine interactions in 3R-AgFeO2 and its structural analogue CuFeO2 points to a specific role played by the topology of the exchange coupling and the oxygen polarization in the delafossite-like structures.

A Comparative Study of Gold Bonding via Electronic Spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Ruohan

The bonding and electrostatic properties of gold containing molecules are highly influenced by relativistic effects. To understand this facet on bonding, a series of simple diatomic AuX (X=F, Cl, O and S) molecules, where upon bond formation the Au atom donates or accepts electrons, was investigated and discussed in this thesis. First, the optical field-free, Stark, and Zeeman spectroscopic studies have been performed on AuF and AuCl. The simple polar bonds between Au and typical halogens (i.e. F and Cl) can be well characterized by the electronic structure studies and the permanent electric dipole moments, mu el. The spectroscopic parameters have been precisely determined for the [17.7]1, [17.8]0+ and X1Sigma + states of AuF, and the [17.07]1, [17.20]0+ and X1Sigma+ states of AuCl. The mu el have been determined for ground and excited states of AuF and AuCl. The results from the hyperfine analysis and Stark measurement support the assignments that the [17.7]1 and [17.8]0+ states of AuF are the components of a 3pi state. Similarly, the analysis demonstrated the [19.07]1 and [19.20]0+ states are the components of the 3pi state of AuCl. Second, my study focused on AuO and AuS because the bonding between gold and sulfur/oxygen is a key component to numerous established and emerging technologies that have applications as far ranging as medical imaging, catalysis, electronics, and material science. The high-resolution spectra were record and analyzed to obtain the geometric and electronic structural data for the ground and excited states. The electric dipole moment, muel , and the magnetic dipole moment, mum, has been the precisely measured by applying external static electric and magnetic fields. muel and mum are used to give insight into the unusual complex bonding in these molecules. In addition to direct studies on the gold-containing molecules, other studies of related molecules are included here as well. These works contain the pure rotation measurement of PtC, the hyperfine and Stark spectroscopic studies of PtF, and the Stark and Zeeman spectroscopic studies of MgH and MgD. Finally, a perspective discussion and conclusion will summarize the results of AuF, AuCl, AuO, and AuS from this work (bond lengths, dipole moment, etc.). The highly quantitative information derived from this work is the foundation of a chemical description of matter and essential for kinetic energy manipulation via Stark and Zeeman interactions. This data set also establishes a synergism with computation chemists who are developing new methodologies for treating relativistic effects and electron correlation.

Paramagnetic species on catalytic surfaces--DFT investigations into structure sensitivity of the hyperfine coupling constants.

PubMed

Sojka, Zbigniew; Pietrzyk, Piotr

2004-05-01

Structure sensitivity of the hyperfine coupling constants was investigated by means of DFT calculations for selected surface paramagnetic species. A *CH2OH radical trapped on silica and intrazeolite copper nitrosyl adducts encaged in ZSM-5 were taken as the examples. The surface of amorphous silica was modeled with a [Si5O8H10] cluster, whereas the zeolite hosting sites were epitomized by [Si4AlO5(OH)10]- cluster. Three different coordination modes of the *CH2OH radical were considered and the isotropic 13C and 1H hyperfine constants of the resultant van der Waals complexes, calculated with B3LYP/6-311G(d), were discussed in terms of the angular deformations caused by hydrogen bonds with the cluster. The magnetic parameters of the eta1-N[CuNO]11 and eta1-O[CuNO]11 linkage isomers were calculated at the BPW91/LanL2DZ and 6-311G(df) level. For the most stable eta1-N adduct a clear dependence of the spin density distribution within the Cu-NO moiety on changes in the Cu-N-O angle and the Cu-N bond distance was observed and accounted for by varying spin polarization and delocalization contributions.

Rolf Landauer and Charles H. Bennett Award Talk: Experimental development of spin qubits in silicon

NASA Astrophysics Data System (ADS)

Morello, Andrea

The modern information era is built on silicon nanoelectronic devices. The future quantum information era might be built on silicon too, if we succeed in controlling the interactions between individual spins hosted in silicon nanostructures. Spins in silicon constitute excellent solid-state qubits, because of the weak spin-orbit coupling and the possibility to remove nuclear spins from the environment through 28Si isotopic enrichment. Substitutional 31P atoms in silicon behave approximately like hydrogen in vacuum, providing two spin 1/2 qubits - the donor-bound electron and the 31P nucleus - that can be coherently controlled, read out in single-shot, and are naturally coupled through the hyperfine interaction. In isotopically-enriched 28Si, these single-atom qubits have demonstrated outstanding coherence times, up to 35 seconds for the nuclear spin, and 1-qubit gate fidelities well above 99.9% for both the electron and the nucleus. The hyperfine coupling provides a built-in interaction to entangle the two qubits within one atom. The combined initialization, control and readout fidelities result in a violation of Bell's inequality with S = 2 . 70 , a record value for solid-state qubits. Despite being identical atomic systems, 31P atoms can be addressed individually by locally modifying the hyperfine interaction through electrostatic gating. Multi-qubit logic gates can be mediated either by the exchange interaction or by electric dipole coupling. Scaling up beyond a single atom presents formidable challenges, but provides a pathway to building quantum processors that are compatible with standard semiconductor fabrication, and retain a nanometric footprint, important for truly large-scale quantum computers. Work supported by US Army Research Office (W911NF-13-1-0024) and Australian Research Council (CE110001027).

Zeeman interaction in the Δ31 state of HfF+ to search for the electron electric dipole moment

NASA Astrophysics Data System (ADS)

Petrov, A. N.; Skripnikov, L. V.; Titov, A. V.

2017-08-01

A theoretical study devoted to suppression of magnetic systematic effects in HfF+ cation for an experiment to search for the electron electric dipole moment is reported. The g factors for J =1 , F =3 /2 , | MF|=3 /2 hyperfine levels of the Δ31 state are calculated as functions of the external electric field. The minimal value for the difference between the g factors of Ω -doublet levels, Δ g =3 ×10-6 , is attained at the electric field 7 V/cm. The body-fixed g factor, G∥, was obtained both within the ab initio electronic structure calculations and with our fit of the experimental data [H. Loh, K. C. Cossel, M. C. Grau, K.-K. Ni, E. R. Meyer, J. L. Bohn, J. Ye, and E. A. Cornell, Science 342, 1220 (2013), 10.1126/science.1243683]. For the electronic structure calculations we used a combined scheme to perform correlation calculations of HfF+, which includes both the direct four-component all-electron and generalized relativistic effective core potential approaches. The electron correlation effects were treated using the coupled cluster methods. The calculated value G∥=0.0115 agrees very well with the G∥=0.0118 obtained with our fitting procedure. The calculated ab initio value D∥=-1.53 a.u. for the molecule-frame dipole moment (with the origin in the center of mass) is in agreement with the experimental datum D∥=-1.54 (1 ) a.u. [H. Loh, Ph.D. thesis, Massachusetts Institute of Technology, 2006.].

Anomalous behavior of the magnetic hyperfine field at 140Ce impurities at La sites in LaMnSi2

NASA Astrophysics Data System (ADS)

Domienikan, C.; Bosch-Santos, B.; Cabrera-Pasca, G. A.; Saxena, R. N.; Carbonari, A. W.

2018-05-01

Magnetic hyperfine field has been measured in the orthorhombic intermetallic compound LaMnSi2 with perturbed angular correlation (PAC) spectroscopy using radioactive 140La(140Ce) nuclear probes. Magnetization measurements were also carried out in this compound with MPSM-SQUID magnetometer. Samples of LaMnSi2 compound were prepared by arc melting the component metals with high purity under argon atmosphere followed by annealing at 1000°C for 60 h under helium atmosphere and quenching in water. X-ray analysis confirmed the samples to be in a single phase with correct crystal structure expected for LaMnSi2 compound. The radioactive 140La (T1/2 = 40 h) nuclei were produced by direct irradiation of the sample with neutrons in the IEA-R1 nuclear research reactor at IPEN with a flux of ˜ 1013 n cm-2s-1 for about 3 - 4 min. The PAC measurements were carried out with a six BaF2 detector spectrometer at several temperatures between 10 K and 400 K. Temperature dependence of the hyperfine field, Bhf was found to be anomalous. A modified two-state model explained this anomalous behavior where the effective magnetic hyperfine field at 140Ce is believed to have two contributions, one from the unstable localized spins at Ce impurities and another from the magnetic Mn atoms of the host. The competition of these two contributions explains the anomalous behavior observed for the temperature dependence of the magnetic hyperfine field at 140Ce. The ferromagnetic transition temperature (TC) of LaMnSi2 was determined to be 400(1) K confirming the magnetic measurements.

Effect of thermal history on Mossbauer signature and hyperfine interaction parameters of copper ferrite

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

Modi, K. B., E-mail: kunalbmodi2003@yahoo.com; Raval, P. Y.; Dulera, S. V.

Two specimens of copper ferrite, CuFe{sub 2}O{sub 4}, have been synthesized by double sintering ceramic technique with different thermal history i.e. slow cooled and quenched. X-ray diffractometry has confirmed single phase fcc spinel structure for slow cooled sample while tetragonal distortion is present in quenched sample. Mossbauer spectral analysis for slow-cooled copper ferrite reveals super position of two Zeeman split sextets along with paramagnetic singlet in the centre position corresponds to delafossite (CuFeO{sub 2}) phase that is completely absent in quenched sample. The hyperfine interaction parameters are highly influenced by heat treatment employed.

The millimeter and submillimeter rotational spectrum of the MgCN radical (X (sup 2) Sigma(+))

NASA Technical Reports Server (NTRS)

Anderson, M. A.; Steimle, T. C.; Ziurys, L. M.

1994-01-01

The pure rotational spectrum of the MgCN radical has been recorded in the laboratory using millimeter/submillimeter direct absorption spectroscopy. Twenty-seven rotational transitions of the species were observed in the range 101-376 GHz and indicate that the molecule is linear with a (sup 2)Sigma(+) ground electronic state, as predicted by theory. Spin rotation interactions were resolved in the spectra, but no hyperfine splittings were observed, which would originate with the nitrogen nuclear spin. The rotational and fine-structure constants were determined for this radical from a nonlinear least-squares fit to the data using a (sup 2)Sigma Hamiltonian. MgCN is of astrophysical interest because it is the metastable isomer of MgNC, which recently has been detected toward IRC +10216

Electron paramagnetic resonance of deep boron in silicon carbide

NASA Astrophysics Data System (ADS)

Baranov, P. G.; Mokhov, E. N.

1996-04-01

In this article we report the first EPR observation of deep boron centres in silicon carbide. A direct identification of the boron atom involved in the defect centre, considered as deep boron, has been established by the presence of a hyperfine interaction with 0268-1242/11/4/005/img1 and 0268-1242/11/4/005/img2 nuclei in isotope-enriched 6H-SiC:B crystals. Deep boron centres were shown from EPR spectra to have axial symmetry along the hexagonal axis. A correspondence between the EPR spectra and the luminescence, ODMR and DLTS spectra of deep boron centres has been indicated. The structural model for a deep boron centre as a boron - vacancy pair is presented and the evidence for bistable behaviour of deep boron centres is discussed.

EPR of radiation defects in lithium-oxyfluoride glass ceramics

NASA Astrophysics Data System (ADS)

Fedotovs, A.; Rogulis, U.; Sarakovskis, A.; Dimitrocenko, L.

2010-11-01

We studied oxyfluoride composites based on lithium silicate glasses with yttrium fluorides and rare-earth dopants. The electron paramagnetic resonance (EPR) has been used to obtain information about radiation induced defects in these materials. Spectra have been measured before and after X-ray irradiation at room temperature and at liquid nitrogen temperature. Fluoride crystallites within samples were created by means of thermal treatment at specific temperatures. EPR spectra of radiation induced defects in oxyfluoride glass ceramics, in which crystallites have not been yet created, show no explicit hfs interaction of fluorine nuclei. However, in glass ceramics, which already contains fluoride crystallites, the hfs characteristic to fluorine nuclei appears in the EPR spectra. EPR hyperfine structure could be explained within a model of an F-type centre in YF3 crystalline phase.

Nanoscale cluster dynamics in the martensitic phase of Ni-Mn-Sn shape-memory alloys

NASA Astrophysics Data System (ADS)

Hoch, Michael; Yuan, Shaojie; Kuhns, Phillip; Reyes, Arneil; Brooks, James; Phelan, Daniel; Srivastava, Vijay; James, Richard; Leighton, Chris

2015-03-01

The martensitic phases of Ni-Mn-Sn magnetic shape memory alloys exhibit interesting low temperature magnetic properties, including intrinsic superparamagnetism and exchange bias effects, which have previously been rationalized in terms of spin clusters. We show here that spin-echo NMR, involving 55Mn hyperfine fields, permits ferromagnetic and antiferromagnetic nanoregions to be directly identified in these materials and yields estimates of their size distributions. Nuclear relaxation rate measurements, made as a function of temperature, provide information on both the dynamics and on the electronic structure of the nanoregions. The relaxation rates are analyzed using a combination of Redfield and Korringa mechanisms, the Korringa procedure providing information on the density of states at the Fermi level. Results will be presented for a number of these alloys. DMR-1309463.

THE HYPERFINE STRUCTURE OF THE ROTATIONAL SPECTRUM OF HDO AND ITS EXTENSION TO THE THz REGION: ACCURATE REST FREQUENCIES AND SPECTROSCOPIC PARAMETERS FOR ASTROPHYSICAL OBSERVATIONS

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

Cazzoli, Gabriele; Lattanzi, Valerio; Puzzarini, Cristina

2015-06-10

The rotational spectrum of the mono-deuterated isotopologue of water, HD{sup 16}O, has been investigated in the millimeter- and submillimeter-wave frequency regions, up to 1.6 THz. The Lamb-dip technique has been exploited to obtain sub-Doppler resolution and to resolve the hyperfine (hf) structure due to the deuterium and hydrogen nuclei, thus enabling the accurate determination of the corresponding hf parameters. Their experimental determination has been supported by high-level quantum-chemical calculations. The Lamb-dip measurements have been supplemented by Doppler-limited measurements (weak high-J and high-frequency transitions) in order to extend the predictive capability of the available spectroscopic constants. The possibility of resolving hfmore » splittings in astronomical spectra has been discussed.« less

Hyperfine structure of atomic fluorine (F I)

NASA Astrophysics Data System (ADS)

Huo, Xiaoxue; Deng, Lunhua; Windholz, L.; Mu, Xiuli; Wang, Hailing

2018-01-01

A high resolution absorption spectrum of neutral fluorine(F I) was observed around 800 nm using concentration modulation absorption spectroscopy with a tunable Ti : Sapphire laser. The fluorine atoms were produced by discharging the mixed gases of helium and sulfur hexafluoride (SF6) in a glass tube. Thirty four hyperfine structure (hfs) resolved transitions were analyzed to obtain 23 magnetic dipole hfs constants A for 2p4(3P)3s, 2p4(3P)3p and 2p4(3P)3d configurations. The hfs constants in 2p4(3P)3s and 2p4(3P)3p configurations were compared with those obtained from experiments and calculations. Fifteen constants in 2p4(3P)3d configuration were reported - to our knowledge - for the first time.

Fine Structure in Helium-like Fluorine by Fast-Beam Laser Spectroscopy

NASA Astrophysics Data System (ADS)

Myers, E. G.; Thompson, J. K.; Silver, J. D.

1998-05-01

With the aim of providing an additional precise test of higher-order corrections to high precision calculations of fine structure in helium and helium-like ions(T. Zhang, Z.-C. Yan and G.W.F. Drake, Phys. Rev. Lett. 77), 1715 (1996)., a measurement of the 2^3P_2,F - 2^3P_1,F' fine structure in ^19F^7+ is in progress. The method involves doppler-tuned laser spectroscopy using a CO2 laser on a foil-stripped fluorine ion beam. We aim to achieve a higher precision, compared to an earlier measurement(E.G. Myers, P. Kuske, H.J. Andrae, I.A. Armour, H.A. Klein, J.D. Silver, and E. Traebert, Phys. Rev. Lett. 47), 87 (1981)., by using laser beams parallel and anti-parallel to the ion beam, to obtain partial cancellation of the doppler shift(J.K. Thompson, D.J.H. Howie and E.G. Myers, Phys. Rev. A 57), 180 (1998).. A calculation of the hyperfine structure, allowing for relativistic, QED and nuclear size effects, will be required to obtain the ``hyperfine-free'' fine structure interval from the measurements.

Lithium formate for EPR dosimetry: radiation-induced radical trapping at low temperatures.

PubMed

Krivokapić, André; Aalbergsjø, Siv G; De Cooman, Hendrik; Hole, Eli Olaug; Nelson, William H; Sagstuen, Einar

2014-05-01

Radiation-induced primary radicals in lithium formate. A material used in EPR dosimetry have been studied using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and ENDOR-Induced EPR (EIE) techniques. In this study, single crystals were X irradiated at 6-8 K and radical formation at these and higher temperatures were investigated. Periodic density functional theory calculations were used to assist in assigning the radical structures. Mainly two radicals are present at 6 K, the well-known CO2(•-) radical and a protonated electron-gain product. Hyperfine coupling tensors for proton and lithium interactions were obtained for these two radicals and show that the latter radical exists in four conformations with various degrees of bending at the radical center. Pairs of CO2(•-) radicals were also observed and the tensor for the electron-electron dipolar coupling was determined for the strongest coupled pair, which exhibited the largest spectral intensity. Upon warming, both the radical pairs and the reduction product decay, the latter apparently by a transient species. Above 200 K the EPR spectrum was mainly due to the CO2(•-) (mono) radicals, which were previously characterized as the dominant species present at room temperature and which account for the dosimetric EPR signal.

Comment on "Electron spin resonance studies in β-FeSi2 crystals" [J. Appl. Phys. 80, 1678 (1996)

NASA Astrophysics Data System (ADS)

Irmscher, K.; Gehlhoff, W.; Lange, H.

1997-06-01

In a recent article [J. Appl. Phys. 80, 1678 (1996)] Aksenov et al. reported on electron paramagnetic resonance (EPR) studies in β-FeSi2 crystals grown by chemical vapor transport. They did not perform a rigorous measurement of the angular variation of the EPR line positions. Consequently, there has been a drastic loss of information and most of their conclusions turn out to be erroneous. It is shown that the anisotropic signals (Ai,Bi) do not arise from spin triplet states but from centers with S=1/2 and their origins are not Ni2+ ions but Ni+ (Ai) and Cr- (Bi) ions substituting for Fe on one of its two inequivalent lattice sites. The analysis of the line structure of the isotropic signal (C) is incorrect and hence, the structure cannot be attributed to a ligand hyperfine interaction with four iron atoms. Finally, the determination of an acceptor activation energy from the temperature dependence of the C signal is not justified since no correction for the EPR intensity dependence due to the thermal population difference of the Zeeman levels was included.

Structural investigations of vanadyl doped Nb2O5·K2O·B2O3 glasses

NASA Astrophysics Data System (ADS)

Anshu; Sanghi, S.; Agarwal, A.; Lather, M.; Bhatnagar, V.; Khasa, S.

2009-07-01

Pottasium nioborate glasses of composition xNb2O5·(30-x)K2O·69B2O3 containing 1 mol % of V2O5 were prepared by melt quench technique (1473K, 1h). The electron paramagnetic resonance spectra of VO2+ in these glasses have been recorded in X- band (v approx 9.14 GHz) at room temperature (RT). The spin Hamiltonian parameters, dipolar hyperfine coupling parameters, P and Fermi contact interaction parameter, K have been calculated. It is found that V4+ ions in these glasses exist as VO2+ in octahedral coordination with a tetragonal distortion. The tetragonality of V4+O6 complex decreases with increasing Nb2O5: K2O ratio and also there is an expansion of 3dXY orbit of unpaired electron in the vanadium ion. The study of IR transmission spectra over a range 400- 4000 cm-1 depicts the presence of both BO3 and BO4 structural units and Nb5+ ions are incorporated into the glass network as NbO6 octahedra, substituting BO4 groups.

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

Utschig, L. M.; Dalosto, S. D.; Thurnauer, M. C.

Metal ion binding to a surface site on photosynthetic reaction centers (RCs) modulates light-induced electron and proton transfer events in the RC. Whereas many studies have elucidated aspects of metal ion modulation events in Rhodobacter sphaeroides RCs, much less is understood about the surface site in Blastochloris viridis (Blc. viridis) RCs. Interestingly, electron paramagnetic resonance studies revealed two spectroscopically distinct Cu{sup 2+} surface site environments in Blc. viridis RCs. Herein, Cu{sup 2+} has been used to spectroscopically probe the structure of these Cu{sup 2+} site(s) in response to freezing conditions, temperature, and charge separation. One Cu{sup 2+} environment in Blc.more » viridis RCs, termed CuA, exhibits temperature-dependent conformational flexibility. Different conformation states of the CuA{sup 2+} site are trapped when the RC is frozen in the dark either by fast-freeze or slow-freeze procedure. The second Cu{sup 2+} environment, termed CuB, is structurally invariant to different freezing conditions and shows resolved hyperfine coupling to three nitrogen atoms. Cu{sup 2+} is most likely binding at the same location on the RC, but in different coordination environments which may reflect two distinct conformational states of the isolated Blc. viridis RC protein.« less

Hyperfine Fields of 181Ta in UFe4Al8

NASA Astrophysics Data System (ADS)

Marques, J. G.; Barradas, N. P.; Alves, E.; Ramos, A. R.; Gonçalves, A. P.; da Silva, M. F.; Soares, J. C.

2001-11-01

The γ γ Perturbed Angular Correlation technique was used to study the hyperfine interaction of 181Ta at the Hf site(s) in UFe4Al8 at room temperature and 12 K. The data at room temperature are well described by two electric field gradients, while at low temperature two combined hyperfine interactions have to be considered, one with the magnetic hyperfine field collinear with the c-axis and another with the magnetic hyperfine field in the basal plane. The results are compared with previous Mössbauer and neutron diffraction experiments and the lattice site of Hf is discussed.

Hyperfine interactions and electric dipole moments in the [16.0]1.5(v = 6), [16.0]3.5(v = 7), and X2Δ(5/2) states of iridium monosilicide, IrSi.

PubMed

Le, Anh; Steimle, Timothy C; Morse, Michael D; Garcia, Maria A; Cheng, Lan; Stanton, John F

2013-12-19

The (6,0)[16.0]1.5-X(2)Δ(5/2) and (7,0)[16.0]3.5-X(2)Δ(5/2) bands of IrSi have been recorded using high-resolution laser-induced fluorescence spectroscopy. The field-free spectra of the (191)IrSi and (193)IrSi isotopologues were modeled to generate a set of fine, magnetic hyperfine, and nuclear quadrupole hyperfine parameters for the X(2)Δ(5/2)(v = 0), [16.0]1.5(v = 6), and [16.0]3.5 (v = 7) states. The observed optical Stark shifts for the (193)IrSi and (191)IrSi isotopologues were analyzed to produce the permanent electric dipole moments, μ(el), of -0.414(6) D and 0.782(6) D for the X(2)Δ(5/2) and [16.0]1.5 (v = 6) states, respectively. Properties of the X(2)Δ(5/2) state computed using relativistic coupled-cluster methods clearly indicate that electron correlation plays an essential role. Specifically, inclusion of correlation changes the sign of the dipole moment and is essential for achieving good accuracy for the nuclear quadrupole coupling parameter eQq0.

Measurement of the 1s Hyperfine Transition of Two Tl^80+ Isotopes

NASA Astrophysics Data System (ADS)

Beiersdorfer, P.; Utter, S. B.; Wong, K. L.; Crespo López-Urrutia, J. R.; Britten, J. A.; Chen, H.; Thoe, R. S.; Thorn, D. B.; Träbert, E.; Gustavsson, M. G. H.; Forssén, C.; Mårtenson-Pendrill, A.-M.; Harris, C. L.

2001-05-01

The hyperfine splitting of the 1s ground state has been measured for the two stable isotopes of hydrogen-like Tl using emission spectroscopy in the SuperEBIT electron beam ion trap. The results are 3858.22± 0.30 Åfor ^203Tl^80+ and 3821.84± 0.34 Åfor ^205Tl^80+. These differ by about 60 Å from recent and about 19 Å from very recent calculations, illustrating unsolved issues affecting these transitions in hydrogen-like ions. The wavelength difference Δλ = 36.38± 0.35 Å is consistent with estimates based on hyperfine anomaly data for neutral Tl. By using previously determined nuclear magnetic moments and applying appropriate corrections for the nuclear charge distribution and radiative effects, the experimental splittings can be interpreted in terms of nuclear magnetization radii < r^2_m>^1/2= 5.83(14) fm for ^203Tl and < r^2_m>^1/2= 5.89(14) fm for ^205Tl. These values are 10% larger than derived from single-particle nuclear magnetization models, and are slightly larger than the corresponding charge distributions. *Work performed under the auspices of DOE by UCLLNL under contract W-7405-ENG-48 and supported by the Office of Basic Energy Sciences.

Hyperfine induced transition probabilities from 4{f}^{14}5s5p{}^{3}{{\\rm{P}}}_{0,2}^{o} states in Sm-like ions

NASA Astrophysics Data System (ADS)

Zhou, Fuyang; Li, Jiguang; Qu, Yizhi; Wang, Jianguo

2017-11-01

The hyperfine induced 4{f}145s5p{}3{{{P}}}0,2o-4{f}145{s}2{}1{{{S}}}0 transition probabilities for highly charged Sm-like ions are calculated within the framework of the multiconfiguration Dirac-Hartree-Fock method. Electron correlation, the Breit interaction and quantum electrodynamical effects are taken into account. For ions ranging from Z = 79 to Z=94,4{f}145s5p{}3{{{P}}}0o is the first excited state, and the hyperfine induced transition (HIT) is a dominant decay channel. For the 4{f}145s5p{}3{{{P}}}2o state, the HIT rates of Sm-like ions with Z=82-94 are reported as well as the magnetic dipole (M1) {}3{{{P}}}2o-{}3{{{P}}}1o, the electric quadrupole (E2) {}3{{{P}}}2o-{}3{{{P}}}0,1o, and the magnetic quadrupole (M2) {}3{{{P}}}2o-{}1{{{S}}}0 transition probabilities. It is found that M1 transition from the 4{f}145s5p{}3{{{P}}}2o state is the most important decay channel in this range on Z≥slant 82.

Muon contact hyperfine field in metals: A DFT calculation

NASA Astrophysics Data System (ADS)

Onuorah, Ifeanyi John; Bonfà, Pietro; De Renzi, Roberto

2018-05-01

In positive muon spin rotation and relaxation spectroscopy it is becoming customary to take advantage of density functional theory (DFT) based computational methods to aid the experimental data analysis. DFT-aided muon site determination is especially useful for measurements performed in magnetic materials, where large contact hyperfine interactions may arise. Here we present a systematic analysis of the accuracy of the ab initio estimation of muon's hyperfine contact field on elemental transition metals, performing state-of-the-art spin-polarized plane-wave DFT and using the projector-augmented pseudopotential approach, which allows one to include the core state effects due to the spin ordering. We further validate this method in not-so-simple, noncentrosymmetric metallic compounds, presently of topical interest for their spiral magnetic structure giving rise to skyrmion phases, such as MnSi and MnGe. The calculated hyperfine fields agree with experimental values in all cases, provided the spontaneous spin magnetization of the metal is well reproduced within the approach. To overcome the known limits of the conventional mean-field approximation of DFT on itinerant magnets, we adopt the so-called reduced Stoner theory [L. Ortenzi et al., Phys. Rev. B 86, 064437 (2012), 10.1103/PhysRevB.86.064437]. We establish the accuracy of the estimated muon contact field in metallic compounds with DFT and our results show improved agreement with experiments compared to those of earlier publications.

Generation, Detection and characterization of Gas-Phase Transition Metal containing Molecules

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

Steimle, Timothy

The objective of this project was to generate, detect, and characterize small, gas-phase, metal containing molecules. In addition to being relevant to high temperature chemical environments (e.g. plasmas and combustion), gas-phase experiments on metal containing molecules serve as the most direct link to a molecular-level theoretical model for catalysis. Catalysis (i.e. the addition of a small about of recoverable material to control the rate and direction of a chemical reaction) is critical to the petroleum and pharmaceutical industries as well as environmental remediation. Currently, the majority of catalytic materials are based on very expensive metals such as platinum (Pt), palladiummore » (Pd), iridium (Ir,) rhenium (Re), and rhodium (Rh). For example, the catalyst used for converting linear hydrocarbon molecules (e.g. hexane) to cyclic molecules (e.g. cyclohexane) is a mixture of Pt and Re suspended on alumina. It enables straight chain alkanes to be converted into branched-chain alkanes, cyclohexanes and aromatic hydrocarbons which are used, amongst other things, to enhance the octane number of petrol. A second example is the heterogeneous catalysis used in automobile exhaust systems to: a) decrease nitrogen oxide; b) reduce carbon monoxide; and c) oxidize unburned hydrocarbons. The exhaust is vented through a high-surface area chamber lined with Pt, Pd, and Rh. For example, the carbon monoxide is catalytically converted to carbon dioxide by reaction with oxygen. The research results from this work have been published in readily accessible journals1-28. The ground and excited electronic state properties of small metal containing molecules that we determine were: a) electronic state distributions and lifetimes, b) vibrational frequencies, c) bond lengths and angles, d) hyperfine interactions, e) permanent electric dipole moments, mel, and f) magnetic dipoles, μ m. In general terms, μ el, gives insight into the charge distribution and mm into the number and nature of the unpaired electrons. Analysis of the hyperfine interactions (i.e. Fermi-contact, nuclear electric quadrupole, etc.) is particularly insightful because it results from the interaction of nuclei with non-zero spin and the chemically important valence electrons. The bulk of the spectroscopic techniques used in these studies exploit the sensitivity of laser induced fluorescence (LIF) detection. The spectroscopic schemes employed include: a) cw and pulsed laser field-free(FF) excitation and dispersed LIF (DLIF); b) optical Stark; c) optical Zeeman; d) pump/probe microwave double resonance (PPMODR); e) fluorescence lifetimes, and f) resonant and non-resonant two-photon ionization TOF mass spectrometry. Vibrational spacing, force constants and electronic states distributions are derived from the analysis of pulsed dye laser excitation and DLIF spectra. Geometric structure (bond lengths and angles) and hyperfine parameters are derived from the analysis of cw-laser LIF and PPMODR spectra. Permanent electric dipole moments, mel,, and magnetic dipole moments, mm, are derived from the analysis of optical Stark and Zeeman spectra, respectively. Transition moments are derived from the analysis of radiative lifetimes. A supersonic molecular beam sample of these ephemeral molecules is generated by skimming the products of either a laser ablation/reaction source or a d.c. discharge source.« less

Hyperfine interaction in the Autler-Townes effect: The formation of bright, dark, and chameleon states

NASA Astrophysics Data System (ADS)

Kirova, T.; Cinins, A.; Efimov, D. K.; Bruvelis, M.; Miculis, K.; Bezuglov, N. N.; Auzinsh, M.; Ryabtsev, I. I.; Ekers, A.

2017-10-01

This paper is devoted to clarifying the implications of hyperfine (HF) interaction in the formation of adiabatic (i.e., "laser-dressed") states and their expression in the Autler-Townes (AT) spectra. We first use the Morris-Shore model [J. R. Morris and B. W. Shore, Phys. Rev. A 27, 906 (1983), 10.1103/PhysRevA.27.906] to illustrate how bright and dark states are formed in a simple reference system where closely spaced energy levels are coupled to a single state with a strong laser field with the respective Rabi frequency ΩS. We then expand the simulations to realistic hyperfine level systems in Na atoms for a more general case when non-negligible HF interaction can be treated as a perturbation in the total system Hamiltonian. A numerical analysis of the adiabatic states that are formed by coupling of the 3 p3 /2 and 4 d5 /2 states by the strong laser field and probed by a weak laser field on the 3 s1 /2-3 p3 /2 transition yielded two important conclusions. Firstly, the perturbation introduced by the HF interaction leads to the observation of what we term "chameleon" states—states that change their appearance in the AT spectrum, behaving as bright states at small to moderate ΩS, and fading from the spectrum similarly to dark states when ΩS is much larger than the HF splitting of the 3 p3 /2 state. Secondly, excitation by the probe field from two different HF levels of the ground state allows one to address orthogonal sets of adiabatic states; this enables, with appropriate choice of ΩS and the involved quantum states, a selective excitation of otherwise unresolved hyperfine levels in excited electronic states.

A review of atomic clock technology, the performance capability of present spaceborne and terrestrial atomic clocks, and a look toward the future

NASA Technical Reports Server (NTRS)

Vessot, Robert F. C.

1989-01-01

Clocks have played a strong role in the development of general relativity. The concept of the proper clock is presently best realized by atomic clocks, whose development as precision instruments has evolved very rapidly in the last decades. To put a historical prospective on this progress since the year AD 1000, the time stability of various clocks expressed in terms of seconds of time error over one day of operation is shown. This stability of operation must not be confused with accuracy. Stability refers to the constancy of a clock operation as compared to that of some other clocks that serve as time references. Accuracy, on the other hand, is the ability to reproduce a previously defined frequency. The issues are outlined that must be considered when accuracy and stability of clocks and oscillators are studied. In general, the most widely used resonances result from the hyperfine interaction of the nuclear magnetic dipole moment and that of the outermost electron, which is characteristic of hydrogen and the alkali atoms. During the past decade hyperfine resonances of ions have also been used. The principal reason for both the accuracy and the stability of atomic clocks is the ability of obtaining very narrow hyperfine transition resonances by isolating the atom in some way so that only the applied stimulating microwave magnetic field is a significant source of perturbation. It is also important to make resonance transitions among hyperfine magnetic sublevels where separation is independent, at least to first order, of the magnetic field. In the case of ions stored in traps operating at high magnetic fields, one selects the trapping field to be consistent with a field-independent transition of the trapped atoms.

Terahertz Spectroscopy of CrH (X 6Σ+) and AlH (X 1Σ+)

NASA Astrophysics Data System (ADS)

Halfen, D. T.; Ziurys, L. M.

2016-12-01

New laboratory measurements of hydrides have been carried out using terahertz direct absorption spectroscopy. Spin components of the N=2≤ftarrow 1 transition of the free radical CrH (X 6Σ+) have been recorded in the range 730-734 GHz, as well as a new measurement of the J=2≤ftarrow 1 line of AlH (X 1Σ+) near 755 GHz. Both species were created in an AC discharge of H2, argon, and metal vapor. For CrH, the chromium source was Cr(CO)6, while AlH was produced from Al(CH3)3. The J=4.5≤ftarrow 3.5 and 3.5≤ftarrow 2.5 fine-structure components were recorded for CrH, each which consists of resolved proton hyperfine doublets. For AlH, the two main quadrupole components, F=4.5≤ftarrow 3.5 and 3.5≤ftarrow 2.5, of the J=2≤ftarrow 1 transition were observed as blended features. These data were analyzed with previous 1≤ftarrow 0 millimeter/submillimeter measurements with 6Σ and 1Σ Hamiltonians for chromium and aluminum hydrides, respectively, and rotational, fine-structure (CrH only), and hyperfine constants were derived. The new measurements have resulted in refined spectroscopic parameters for both species, as well as direct measurement of the respective 2≤ftarrow 1 rotational transitions. This work also resolves a 10 MHz discrepancy in the frequency of the AlH line. CrH and AlH have already been observed in the photospheres of stars via their electronic transitions. These data will facilitate their discovery at submillimeter/terahertz wavelengths in circumstellar envelopes and perhaps in diffuse clouds.

Electrical detection of proton-spin motion in a polymer device at room temperature

NASA Astrophysics Data System (ADS)

Boehme, Christoph

With the emergence of spintronics concepts based on organic semiconductors there has been renewed interest in the role of both, electron as well as nuclear spin states for the magneto-optoelectronic properties of these materials. In spite of decades of research on these molecular systems, there is still much need for an understanding of some of the fundamental properties of spin-controlled charge carrier transport and recombination processes. This presentation focuses on mechanisms that allow proton spin states to influence electronic transition rates in organic semiconductors. Remarkably, even at low-magnetic field conditions and room temperature, nuclear spin states with energy splittings orders of magnitude below thermal energies are able to influence observables like magnetoresistance and fluorescence. While proton spins couple to charge carrier spins via hyperfine interaction, there has been considerable debate about the nature of the electronic processes that are highly susceptible to these weak hyperfine fields. Here, experiments are presented which show how the magnetic resonant manipulation of electron and nuclear spin states in a π-conjugated polymer device causes changes of the device current. The experiments confirm the extraordinary sensitivity of electronic transitions to very weak magnetic field changes and underscore the potential significance of spin-selection rules for highly sensitive absolute magnetic fields sensor concepts. However, the relevance of these magnetic-field sensitive spin-dependent electron transitions is not just limited to semiconductor materials but also radical pair chemistry and even avian magnetoreceptors This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award #DE-SC0000909. The Utah NSF - MRSEC program #DMR 1121252 is acknowledged for instrumentation support.

Computational study of the electronic structure and magnetic properties of the Ni-C state in [NiFe] hydrogenases including the second coordination sphere.

PubMed

Kampa, Mario; Lubitz, Wolfgang; van Gastel, Maurice; Neese, Frank

2012-12-01

[NiFe] hydrogenases catalyze the reversible formation of H(2). The [NiFe] heterobimetallic active site is rich in redox states. Here, we investigate the key catalytic state Ni-C of Desulfovibrio vulgaris Miyazaki F hydrogenase using a cluster model that includes the truncated amino acids of the entire second coordination sphere of the enzyme. The optimized geometries, computed g tensors, hyperfine coupling constants, and IR stretching frequencies all agree well with experimental values. For the hydride in the bridging position, only a single minimum on the potential energy surface is found, indicating that the hydride bridges and binds to both nickel and iron. The influence of the second coordination sphere on the electronic structure is investigated by comparing results from the large cluster models with truncated models. The largest interactions of the second coordination sphere with the active site concern the hydrogen bonds with the cyanide ligands, which modulate the bond between iron and these ligands. Secondly, the electronic structure of the active site is found to be sensitive to the protonation state of His88. This residue forms a hydrogen bond with the spin-carrying sulfur atom of Cys549, which in turn tunes the spin density at the nickel and coordinating sulfur atoms. In addition, the unequal distribution of spin density over the equatorial cysteine residues results from different orientations of the cysteine side chains, which are kept in their particular orientation by the secondary structure of the protein.

DFT and ENDOR Study of Bixin Radical Cations and Neutral Radicals on Silica-Alumina.

PubMed

Tay-Agbozo, Sefadzi S; Krzyaniak, Matthew D; Bowman, Michael K; Street, Shane; Kispert, Lowell D

2015-06-18

Bixin, a carotenoid found in annatto (Bixa orellana), is unique among natural carotenoids by being water-soluble. We stabilized free radicals from bixin on the surface of silica-alumina (Si-Al) and characterized them by pulsed electron-nuclear double resonance (ENDOR). DFT calculations of unpaired electron spin distribution for various bixin radicals predict the EPR hyperfine couplings. Least-square fitting of experimental ENDOR spectra by spectra calculated from DFT hyperfine couplings characterized the radicals trapped on Si-Al. DFT predicts that the trans bixin radical cation is more stable than the cis bixin radical cation by 1.26 kcal/mol. This small energy difference is consistent with the 26% trans and 23% cis radical cations in the ENDOR spectrum. The remainder of the ENDOR spectrum is due to several neutral radicals formed by loss of a H(+) ion from the 9, 9', 13, or 13' methyl group, a common occurrence in all water-insoluble carotenoids previously studied. Although carboxyl groups of bixin strongly affect its solubility relative to other natural carotenoids, they do not alter properties of its free radicals based on DFT calculations and EPR measurements which remain similar to typical water-insoluble carotenoids.

EPR analysis of cyanide complexes of wild-type human neuroglobin and mutants in comparison to horse heart myoglobin.

PubMed

Van Doorslaer, Sabine; Trandafir, Florin; Harmer, Jeffrey R; Moens, Luc; Dewilde, Sylvia

2014-06-01

Electron paramagnetic resonance (EPR) data reveal large differences between the ferric ((13)C-)cyanide complexes of wild-type human neuroglobin (NGB) and its H64Q and F28L point mutants and the cyanide complexes of mammalian myo- and haemoglobin. The point mutations, which involve residues comprising the distal haem pocket in NGB, induce smaller, but still significant changes, related to changes in the stabilization of the cyanide ligand. Furthermore, for the first time, the full (13)C hyperfine tensor of the cyanide carbon of cyanide-ligated horse heart myoglobin (hhMb) was determined using Davies ENDOR (electron nuclear double resonance). Disagreement of these experimental data with earlier predictions based on (13)C NMR data and a theoretical model reveal significant flaws in the model assumptions. The same ENDOR procedure allowed also partial determination of the corresponding (13)C hyperfine tensor of cyanide-ligated NGB and H64QNGB. These (13)C parameters differ significantly from those of cyanide-ligated hhMb and challenge our current theoretical understanding of how the haem environment influences the magnetic parameters obtained by EPR and NMR in cyanide-ligated haem proteins. Copyright © 2014 Elsevier B.V. All rights reserved.

Chirp echo Fourier transform EPR-detected NMR

NASA Astrophysics Data System (ADS)

Wili, Nino; Jeschke, Gunnar

2018-04-01

A new ultra-wide band (UWB) pulse EPR method is introduced for observing all nuclear frequencies of a paramagnetic center in a single shot. It is based on burning spectral holes with a high turning angle (HTA) pulse that excites forbidden transitions and subsequent detection of the hole pattern by a chirp echo. We term this method Chirp Echo Epr SpectroscopY (CHEESY)-detected NMR. The approach is a revival of FT EPR-detected NMR. It yields similar spectra and the same type of information as electron-electron double resonance (ELDOR)-detected NMR, but with a multiplex advantage. We apply CHEESY-detected NMR in Q band to nitroxides and correlate the hyperfine spectrum to the EPR spectrum by varying the frequency of the HTA pulse. Furthermore, a selective π pulse before the HTA pulse allows for detecting hyperfine sublevel correlations between transitions of one nucleus and for elucidating the coupling regime, the same information as revealed by the HYSCORE experiment. This is demonstrated on hexaaquamanganese(II). We expect that CHEESY-detected NMR is generally applicable to disordered systems and that our results further motivate the development of EPR spectrometers capable of coherent UWB excitation and detection, especially at higher fields and frequencies.

Coherent manipulation of mononuclear lanthanide-based single-molecule magnets

NASA Astrophysics Data System (ADS)

Datta, Saiti; Ghosh, Sanhita; Krzystek, Jurek; Hill, Stephen; Del Barco, Enrique; Cardona-Serra, Salvador; Coronado, Eugenio

2010-03-01

Using electron spin echo (ESE) spectroscopy, we report measurements of the longitudinal (T1) and transverse (T2) relaxation times of diluted single-crystals containing recently discovered mononuclear lanthanide-based single-molecule magnets (SMMs) encapsulated in polyoxometallate cages [AlDamen et al. J. Am. Chem. Soc. 130, 8874 -- 8875 (2008)]. This encapsulation offers the potential for preserving bulk SMM properties outside of a crystal, e.g. in molecular spintronic devices. The magnetic anisotropy in these complexes arises from the spin-orbit splitting of the ground state J multiplet of the lanthanide ion in the presence of a ligand field. At low frequencies only hyperfine-split transitions within the lowest ground state ±mJ doublet are observed. Spin relaxation times were measured for a holmium complex, and the results were compared for different hyperfine transitions and crystal dilutions. Clear Rabi oscillations were also observed, indicating that one can manipulate the spin coherently in these complexes.

Combined multifrequency EPR and DFT study of dangling bonds in a-Si:H

NASA Astrophysics Data System (ADS)

Fehr, M.; Schnegg, A.; Rech, B.; Lips, K.; Astakhov, O.; Finger, F.; Pfanner, G.; Freysoldt, C.; Neugebauer, J.; Bittl, R.; Teutloff, C.

2011-12-01

Multifrequency pulsed electron paramagnetic resonance (EPR) spectroscopy using S-, X-, Q-, and W-band frequencies (3.6, 9.7, 34, and 94 GHz, respectively) was employed to study paramagnetic coordination defects in undoped hydrogenated amorphous silicon (a-Si:H). The improved spectral resolution at high magnetic field reveals a rhombic splitting of the g tensor with the following principal values: gx=2.0079, gy=2.0061, and gz=2.0034, and shows pronounced g strain, i.e., the principal values are widely distributed. The multifrequency approach furthermore yields precise 29Si hyperfine data. Density functional theory (DFT) calculations on 26 computer-generated a-Si:H dangling-bond models yielded g values close to the experimental data but deviating hyperfine interaction values. We show that paramagnetic coordination defects in a-Si:H are more delocalized than computer-generated dangling-bond defects and discuss models to explain this discrepancy.

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.

Nuclear polarization study: new frontiers for tests of QED in heavy highly charged ions.

PubMed

Volotka, Andrey V; Plunien, Günter

2014-07-11

A systematic investigation of the nuclear polarization effects in one- and few-electron heavy ions is presented. The nuclear polarization corrections in the zeroth and first orders in 1/Z are evaluated to the binding energies, the hyperfine splitting, and the bound-electron g factor. It is shown that the nuclear polarization contributions can be substantially canceled simultaneously with the rigid nuclear corrections. This allows for new prospects for probing the QED effects in a strong electromagnetic field and the determination of fundamental constants.

High-resolution molecular-beam spectroscopy of NaCN and Na 13CN

NASA Astrophysics Data System (ADS)

van Vaals, J. J.; Meerts, W. Leo; Dymanus, A.

The sodium cyanide molecule was studied by molecular-beam electric-resonance spectroscopy in the microwave region. We used the seeded-beam technique to produce a supersonic beam with strong translational, rotational and vibrational cooling. In the frequency range 9.5-40 GHz we observed and identified for NaCN 186 and for Na 13CN 107 hyperfine transitions in 20 and 16 rotational transitions, respectively, all in the ground vibrational state. The rotational, the five quartic and three sextic centrifugal distortion constants of NaCN are: A″ = 57921.954(7) MHz; B″ = 8369.312(2) MHz, C″ = 7272.712(2) MHz. All quadrupole and several spin-rotation coupling constants for the hyperfine interaction were evaluated. The quadrupole coupling constants (in MHz) for NaCN are: eQq12(Na) = -5.344(5), eQq12 = 2.397(7). eQq12(N) = 2.148(4), eQq12(N) = -4.142(5). From these constants and those of Na 13CN we have determined the principal components of the quadrupole coupling tensor for potassium and nitrogen. The structure of sodium cyanide evaluated from the rotational constants of NaCN and Na 13CN was found to be T shaped, similar to the structure of KCN but completely different from the linear isocyanide configuration of LiNC. The effective structural parameters for sodium cyanide in the ground vibrational state are: rCN = 1.170(4) Å, rNaC = 2.379(15) Å, rN12N = 2.233(15) Å, in gratifying agreement with ab initio calculations. Both the geometrical structure and the hyperfine coupling justify the conclusion that the CN group in gaseous sodium cyanide approximately can be considered as a free CN - ion.

Hydrogen bond network around the semiquinone of the secondary quinone acceptor Q(B) in bacterial photosynthetic reaction centers.

PubMed

Taguchi, Alexander T; O'Malley, Patrick J; Wraight, Colin A; Dikanov, Sergei A

2015-05-07

By utilizing a combined pulsed EPR and DFT approach, the high-resolution structure of the QB site semiquinone (SQB) was determined. The development of such a technique is crucial toward an understanding of protein-bound semiquinones on the structural level, as (i) membrane protein crystallography typically results in low resolution structures, and (ii) obtaining protein crystals in the semiquinone form is rarely feasible. The SQB hydrogen bond network was investigated with Q- (∼34 GHz) and X-band (∼9.7 GHz) pulsed EPR spectroscopy on fully deuterated reactions centers from Rhodobacter sphaeroides. Simulations in the SQB g-tensor reference frame provided the principal values and directions of the H-bond proton hyperfine tensors. Three protons were detected, one with an anisotropic tensor component, T = 4.6 MHz, assigned to the histidine NδH of His-L190, and two others with similar anisotropic constants T = 3.2 and 3.0 MHz assigned to the peptide NpH of Gly-L225 and Ile-L224, respectively. Despite the strong similarity in the peptide couplings, all hyperfine tensors were resolved in the Q-band ENDOR spectra. The Euler angles describing the series of rotations that bring the hyperfine tensors into the SQB g-tensor reference frame were obtained by least-squares fitting of the spectral simulations to the ENDOR data. These Euler angles show the locations of the hydrogen bonded protons with respect to the semiquinone. Our geometry optimized model of SQB used in previous DFT work is in strong agreement with the angular constraints from the spectral simulations, providing the foundation for future joint pulsed EPR and DFT semiquinone structural determinations in other proteins.

Magnetic interactions in NiO at ultrahigh pressure

DOE PAGES

Potapkin, Vasily; Dubrovinsky, Leonid; Sergueev, I.; ...

2016-05-24

Here, magnetic properties of NiO have been studied in the multimegabar pressure range by nuclear forward scattering of synchrotron radiation using the 67.4 keV M ssbauer transition of 61Ni. The observed magnetic hyperfine splitting confirms the antiferromagnetic state of NiO up to 280 GPa, the highest pressure where magnetism has been observed so far, in any material. Remarkably, the hyperfine field increases from 8.47 T at ambient pressure to ~24 T at the highest pressure, ruling out the possibility of a magnetic collapse. A joint x-ray diffraction and extended x-ray-absorption fine structure investigation reveals that NiO remains in a distortedmore » sodium chloride structure in the entire studied pressure range. Ab initio calculations support the experimental observations, and further indicate a complete absence of Mott transition in NiO up to at least 280 GPa.« less

The electronic structure of iron in rhyolitic and basaltic glasses at high pressure

NASA Astrophysics Data System (ADS)

Solomatova, N. V.; Jackson, J. M.; Sturhahn, W.; Roskosz, M.

2016-12-01

The physical properties of silicate melts within the Earth's mantle affect the chemical and thermal evolution of the Earth's interior. To understand melting processes within the Earth, it is imperative to determine the structure of silicate melts at high pressure. It has been proposed that iron-bearing silicate melts may exist in the lower mantle just above the core-mantle boundary [1]. The behavior of iron in mantle melts is poorly understood, but can be experimentally approximated by iron-bearing silicate glasses. Previous studies have conflicting conclusions on whether iron in lower mantle silicate melts goes through a high-spin to low-spin transition [2-4]. Additionally, the average coordination environment of iron in glasses is poorly constrained. XANES experiments on basaltic glasses have demonstrated that both four and six-fold coordinated iron may exist in significant amounts regardless of oxidation state [5] while conventional Mössbauer experiments have observed five-fold coordinated Fe2+ with small amounts of four and six-fold coordinated Fe2+ [6]. In an attempt to resolve these discrepancies, we have measured the hyperfine parameters of iron-bearing rhyolitic glass up to 115 GPa and basaltic glass up to 92 GPa in a neon pressure medium using time-resolved synchrotron Mössbauer spectroscopy at the Advanced Photon Source (Argonne National Laboratory, IL). We observed changes in the hyperfine parameters likely due to coordination changes as a result of increasing pressure. Our results indicate that iron does not undergo a high-spin to low-spin transition within the pressure range investigated. Changes in the electronic configuration, such as the spin state of iron affects the compressibility and thermal properties of melts. With the assumption that silica glasses can be used to model structural behavior in silicate melts, our study predicts that iron in chemically-complex silica-rich melts in the lower mantle likely exists in a high-spin state. Select references: [1] Williams and Garnero, Science 273, 1528-1530 (1996). [2] Nomura et al., Nature 473, 199-202 (2011). [3] Gu et al., Geophys. Res. Lett. 39 (2012). [4] Mao et al., Am. Mineral. 99, 415-423 (2014). [5] Wilke et al., Chem. Geology 220, 143-161 (2005). [6] Cottrell and Kelley Earth Planet. Sci. Lett. 305, 270-282 (2011).

Systematic effects in the HfF+-ion experiment to search for the electron electric dipole moment

NASA Astrophysics Data System (ADS)

Petrov, A. N.

2018-05-01

The energy splittings for J =1 , F =3 /2 , | mF|=3 /2 hyperfine levels of the 3Δ1 electronic state of 180Hf+19F ion are calculated as functions of the external variable electric and magnetic fields within two approaches. In the first one, the transition to the rotating frame is performed, whereas in the second approach, the quantization of rotating electromagnetic field is performed. Calculations are required for understanding possible systematic errors in the experiment to search for the electron electric dipole moment (e EDM ) with the 180Hf+19F ion.

Copper ESEEM and HYSCORE through ultra-wideband chirp EPR spectroscopy.

PubMed

Segawa, Takuya F; Doll, Andrin; Pribitzer, Stephan; Jeschke, Gunnar

2015-07-28

The main limitation of pulse electron paramagnetic resonance (EPR) spectroscopy is its narrow excitation bandwidth. Ultra-wideband (UWB) excitation with frequency-swept chirp pulses over several hundreds of megahertz overcomes this drawback. This allows to excite electron spin echo envelope modulation (ESEEM) from paramagnetic copper centers in crystals, whereas up to now, only ESEEM of ligand nuclei like protons or nitrogens at lower frequencies could be detected. ESEEM spectra are recorded as two-dimensional correlation experiments, since the full digitization of the electron spin echo provides an additional Fourier transform EPR dimension. Thus, UWB hyperfine-sublevel correlation experiments generate a novel three-dimensional EPR-correlated nuclear modulation spectrum.

Hyperfine spin interactions between polarons and nuclei in organic light emitting diodes: Magneto-EL measurements

NASA Astrophysics Data System (ADS)

Crooker, S. A.; Kelley, M. R.; Martinez, N.; Nie, W.; Mohite, A. D.; Smith, D. L.; Tretiak, S.; Ruden, P. P.

2014-03-01

Considerable attention in recent years has focused on the effects of applied magnetic fields on the conductance, photocurrent, electroluminescence (EL), and photoluminescence of nominally nonmagnetic organic semiconductor materials and devices. These magnetic field effects have proven useful in revealing the underlying physical mechanisms and relevant spin interactions that influence the electrical and optical properties in these organic systems (e.g., hyperfine coupling, exchange interactions, and spin-orbit coupling). Here we study the field-dependent properties of organic light-emitting diode (OLEDs) based on MTDATA/LiF/Bphen layered structures, in which exciplex recombination at the interface dominates the EL spectra. Small applied magnetic fields (~10 mT) are found to boost the net EL yield by up to 10%, due to a suppression of the mixing between singlet and triplet polaron pairs which, in turn, arises from hyperfine spin coupling of the polarons to the underlying nuclei of the host molecules. We discuss the dependence of these field-induced effects on the LiF barrier thickness, device bias, and on the orientation of the applied magnetic field, as well as the mechanisms responsible.

Toward laser cooling and trapping lanthanum ions

NASA Astrophysics Data System (ADS)

Olmschenk, Steven; Banner, Patrick; Hankes, Jessie; Nelson, Amanda

2017-04-01

Trapped atomic ions are a leading candidate for applications in quantum information. For scalability and applications in quantum communication, it would be advantageous to interface ions with telecom light. We present progress toward laser cooling doubly-ionized lanthanum, which should require only infrared, telecom-compatible light. Since the hyperfine structure of this ion has not been measured, we are using optogalavanic spectroscopy in a hollow cathode lamp to measure the hyperfine spectrum of transitions in lanthanum. Using laser ablation to directly produce ions from a solid target, we laser cool and trap barium ions, and explore extending this technique to lanthanum ions. This research is supported by the Army Research Office, Research Corporation for Science Advancement, and Denison University.

Self-trapped holes in β-Ga2O3 crystals

NASA Astrophysics Data System (ADS)

Kananen, B. E.; Giles, N. C.; Halliburton, L. E.; Foundos, G. K.; Chang, K. B.; Stevens, K. T.

2017-12-01

We have experimentally observed self-trapped holes (STHs) in a β-Ga2O3 crystal using electron paramagnetic resonance (EPR). These STHs are an intrinsic defect in this wide-band-gap semiconductor and may serve as a significant deterrent to producing usable p-type material. In our study, an as-grown undoped n-type β-Ga2O3 crystal was initially irradiated near room temperature with high-energy neutrons. This produced gallium vacancies (acceptors) and lowered the Fermi level. The STHs (i.e., small polarons) were then formed during a subsequent irradiation at 77 K with x rays. Warming the crystal above 90 K destroyed the STHs. This low thermal stability is a strong indicator that the STH is the correct assignment for these new defects. The S = 1/2 EPR spectrum from the STHs is easily observed near 30 K. A holelike angular dependence of the g matrix (the principal values are 2.0026, 2.0072, and 2.0461) suggests that the defect's unpaired spin is localized on one oxygen ion in a nonbonding p orbital aligned near the a direction in the crystal. The EPR spectrum also has resolved hyperfine structure due to equal and nearly isotropic interactions with 69,71Ga nuclei at two neighboring Ga sites. With the magnetic field along the a direction, the hyperfine parameters are 0.92 mT for the 69Ga nuclei and 1.16 mT for the 71Ga nuclei.

Computational Studies of Magnetically Doped Semiconductor Nanoclusters

NASA Astrophysics Data System (ADS)

Gutsev, Lavrenty Gennady

Spin-polarized unrestricted density functional theory is used to calculate the molecular properties of magnetic semiconductor quantum dots doped with 3d-metal atoms. We calculate total energies of the low spin antiferromagnetically coupled states using a spin-flipping algorithm leading to the broken-symmetry states. Given the novel nature of the materials studied, we simulate experimental observables such as hyperfine couplings, ionization/ energies, electron affinities, first and second order polarizabilities, band gaps and exchange coupling constants. Specifically, we begin our investigation with pure clusters of (CdSe )16 and demonstrate the dependence of molecular observables on geometrical structures. We also show that the many isomers of this cluster are energetically quite closely spaced, and thus it would be necessary to employ a battery of tests to experimentally distinguish them. Next, we discuss Mn-doping into the cage (CdSe)9 cluster as well as the zinc-blende stacking type cluster (CdSe)36. We show that the local exchange coupling mechanism is ligand-mediated superexchange and simulate the isotropic hyperfine constants. Finally, we discuss a novel study where (CdSe)9 is doped with Mn or Fe up to a full replacement of all the Cd's and discuss the transition points for the magnetic behavior and specifically the greatly differing band-gap shifts. We also outline an unexpected pattern in the polarizability of the material as metals are added and compare our results with the results from theoretical studies of the bulk material.

Disorder induced spin coherence in polyfluorene thin film semiconductors

NASA Astrophysics Data System (ADS)

Miller, Richard G.; van Schooten, Kipp; Malissa, Hans; Waters, David P.; Lupton, John M.; Boehme, Christoph

2014-03-01

Charge carrier spins in polymeric organic semiconductors significantly influence magneto-optoelectronic properties of these materials. In particular, spin relaxation times influence magnetoresistance and electroluminescence. We have studied the role of structural and electronic disorder in polaron spin-relaxation times. As a model polymer, we used polyfluorene, which can exist in two distinct morphologies: an amorphous (glassy) and an ordered (beta) phase. The phases can be controlled in thin films by preparation parameters and verified by photoluminescence spectroscopy. We conducted pulsed electrically detected magnetic resonance (pEDMR) measurements to determine spin-dephasing times by transient current measurements under bipolar charge carrier injection conditions and a forward bias. The measurements showed that, contrary to intuition, spin-dephasing times increase with material disorder. We attribute this behavior to a reduction in hyperfine field strength for carriers in the glassy phase due to increased structural disorder in the hydrogenated side chains, leading to longer spin coherence times. We acknowledge support by the Department of Energy, Office of Basic Energy Sciences under Award #DE-SC0000909.

The 2-Methoxy Group Orientation Regulates the Redox Potential Difference between the Primary (QA) and Secondary (QB) Quinones of Type II Bacterial Photosynthetic Reaction Centers.

PubMed

de Almeida, Wagner B; Taguchi, Alexander T; Dikanov, Sergei A; Wraight, Colin A; O'Malley, Patrick J

2014-08-07

Recent studies have shown that only quinones with a 2-methoxy group can act simultaneously as the primary (Q A ) and secondary (Q B ) electron acceptors in photosynthetic reaction centers from purple bacteria such as Rb. sphaeroides . 13 C HYSCORE measurements of the 2-methoxy group in the semiquinone states, SQ A and SQ B , were compared with DFT calculations of the 13 C hyperfine couplings as a function of the 2-methoxy dihedral angle. X-ray structure comparisons support 2-methoxy dihedral angle assignments corresponding to a redox potential gap (Δ E m ) between Q A and Q B of 175-193 mV. A model having a methyl group substituted for the 2-methoxy group exhibits no electron affinity difference. This is consistent with the failure of a 2-methyl ubiquinone analogue to function as Q B in mutant reaction centers with a Δ E m of ∼160-195 mV. The conclusion reached is that the 2-methoxy group is the principal determinant of electron transfer from Q A to Q B in type II photosynthetic reaction centers with ubiquinone serving as both acceptor quinones.

π to σ Radical Tautomerization in One-Electron Oxidized 1-Methylcytosine and its Analogs

PubMed Central

Adhikary, Amitava; Kumar, Anil; Bishop, Casandra T.; Wiegand, Tyler J.; Hindi, Ragda M.; Adhikary, Ananya; Sevilla, Michael D.

2015-01-01

In this work iminyl σ-radical formation in several one-electron oxidized cytosine analogs including 1-MeC, cidofovir, 2′-deoxycytidine (dCyd), and 2′-deoxycytidine 5′-monophosphate (5′-dCMP) were investigated in homogeneous aqueous (D2O or H2O) glassy solutions at low temperatures employing electron spin resonance (ESR) spectroscopy. Employing density functional theory (DFT) (DFT/B3LYP/6-31G* method), the calculated hyperfine coupling constant (HFCC) values of iminyl σ-radical agree quite well with the experimentally observed ones thus confirming its assignment. ESR and DFT studies show that the cytosine-iminyl σ-radical is a tautomer of the deprotonated cytosine π-cation radical (cytosine π-aminyl radical, C(N4-H)•). Employing 1-MeC samples at various pHs ranging ca. 8 to ca. 11, ESR studies show that the tautomeric equilibrium between C(N4-H)• and the iminyl σ-radical at low temperature is too slow to be established without added base. ESR and DFT studies agree that in the iminyl-σ radical, the unpaired spin is localized to the exocyclic nitrogen (N4) in an in-plane pure p-orbital. This gives rise to an anisotropic nitrogen hyperfine coupling (Azz = 40 G) from N4 and a near isotropic β-nitrogen coupling of 9.7 G from the cytosine ring nitrogen at N3. Iminyl σ-radical should exist in its N3-protonated form as the N3-protonated iminyl σ-radical is stabilized in solution by over 30 kcal/mol (ΔG= −32 kcal/mol) over its conjugate base, the N3-deprotonated form. This is the first observation of an isotropic β-hyperfine ring nitrogen coupling in an N-centered DNA-radical. Our theoretical calculations predict that the cytosine iminyl σ-radical can be formed in dsDNA by a radiation-induced ionization–deprotonation process that is only 10 kcal/mol above the lowest energy path. PMID:26237072

Tuning cofactor redox potentials: the 2-methoxy dihedral angle generates a redox potential difference of >160 mV between the primary (Q(A)) and secondary (Q(B)) quinones of the bacterial photosynthetic reaction center.

PubMed

Taguchi, Alexander T; Mattis, Aidas J; O'Malley, Patrick J; Dikanov, Sergei A; Wraight, Colin A

2013-10-15

Only quinones with a 2-methoxy group can act simultaneously as the primary (QA) and secondary (QB) electron acceptors in photosynthetic reaction centers from Rhodobacter sphaeroides. (13)C hyperfine sublevel correlation measurements of the 2-methoxy in the semiquinone states, SQA and SQB, were compared with quantum mechanics calculations of the (13)C couplings as a function of the dihedral angle. X-ray structures support dihedral angle assignments corresponding to a redox potential gap (ΔEm) between QA and QB of ~180 mV. This is consistent with the failure of a ubiquinone analogue lacking the 2-methoxy to function as QB in mutant reaction centers with a ΔEm of ≈160-195 mV.

Framework Stability of Nanocrystalline NaY in Aqueous Solution at Varying pH

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

Petushkov, Anton; Freeman, Jasmine; Larsen, Sarah C.

Nanocrystalline zeolites (with crystal sizes of less than 50 nm) are versatile, porous nanomaterials with potential applications in a broad range of areas including bifunctional catalysis, drug delivery, environmental protection, and sensing, to name a few. The characterization of the properties of nanocrystalline zeolites on a fundamental level is critical to the realization of these innovative applications. Nanocrystalline zeolites have unique surface chemistry that is distinct from conventional microcrystalline zeolite materials and that will result in novel applications. In the proposed work, magnetic resonance techniques (solid state nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR)) will be used tomore » elucidate the structure and reactivity of nanocrystalline zeolites and to motivate bifunctional applications. Density functional theory (DFT) calculations will enhance data interpretation through chemical shift, quadrupole coupling constant, g-value and hyperfine calculations.« less

Three-Photon-Annihilation Contributions to Positronium Energies at Order m α7

NASA Astrophysics Data System (ADS)

Adkins, Gregory S.; Kim, Minji; Parsons, Christian; Fell, Richard N.

2015-12-01

Positronium spectroscopy (n =1 hyperfine splitting, n =2 fine structure, and the 2 S -1 S interval) has reached a precision of order 1 MHz. Vigorous ongoing efforts to improve the experimental results motivate the calculation of the positronium energy levels at order m α7. In this Letter, we present the result for a complete class of such contributions—those involving virtual annihilation of positronium to three photons in an intermediate state. We find an energy shift of 2.6216 (11 )m α7/(n π )3=11.5 /n3 kHz for the spin-triplet S state with principal quantum number n . The corresponding energy shift for true muonium (the μ+μ- bound state) is 2.38 /n3 MHz with an additional -5.33 /n3 MHz coming from electronic vacuum polarization.

Spectroscopic properties of (PVA+ZnO):Mn{sup 2+} polymer films

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

Rani, Ch.; Raju, D. Siva; Bindu, S. Hima

2015-05-15

Electron Paramagnetic Resonance (EPR), optical absorption and infrared spectral studies have been carried out on Mn{sup 2+} ions doped in poly(vinyl alcohol) complexed with zinc oxide polymer films prepared by solution cast technique. The EPR spectra of 1 mol% Mn{sup 2+} ions doped polymer complex (PVA+ZnO) at room temperature exhibit sextet hyperfine structure (hfs), centered at 2.01. The spin-Hamiltonian parameter values indicate that the ground state of Mn{sup 2+} ion in d{sup 5} and the site symmetry around Mn{sup 2+} ions in tetragonally distorted octa hedral site. The optical absorption spectra exhibits two bands centered at 275nm at 437nm. Themore » FTIR spectrum exhibits bands characteristic of stretching and banding vibrations of O-H, C-H and C=C groups.« less

The fine tuning of carotenoid-chlorophyll interactions in light-harvesting complexes: an important requisite to guarantee efficient photoprotection via triplet-triplet energy transfer in the complex balance of the energy transfer processes

NASA Astrophysics Data System (ADS)

Di Valentin, Marilena; Carbonera, Donatella

2017-08-01

Triplet-triplet energy transfer (TTET) from the chlorophyll to the carotenoid triplet state is the process exploited by photosynthetic systems to protect themselves from singlet oxygen formation under light-stress conditions. A deep comprehension of the molecular strategies adopted to guarantee TTET efficiency, while at the same time maintaining minimal energy loss and efficient light-harvesting capability, is still lacking. The paramagnetic nature of the triplet state makes electron paramagnetic resonance (EPR) the method of choice when investigating TTET. In this review, we focus on our extended comparative study of two photosynthetic antenna complexes, the Peridinin-chlorophyll a-protein of dinoflagellates and the light-harvesting complex II of higher plants, in order to point out important aspects of the molecular design adopted in the photoprotection strategy. We have demonstrated that a proper analysis of the EPR data allows one to identify the pigments involved in TTET and, consequently, gain an insight into the structure of the photoprotective sites. The structural information has been complemented by a detailed description of the electronic structure provided by hyperfine spectroscopy. All these elements represent the fundamental building blocks toward a deeper understanding of the requirements for efficient photoprotection, which is fundamental to guarantee the prolonged energy conversion action of photosynthesis.

Electron-impact excitation of diatomic hydride cations II: OH+ and SH+

NASA Astrophysics Data System (ADS)

Hamilton, James R.; Faure, Alexandre; Tennyson, Jonathan

2018-05-01

R-matrix calculations combined with the adiabatic-nuclei-rotation and Coulomb-Born approximations are used to compute electron-impact rotational rate coefficients for two open-shell diatomic cations of astrophysical interest: the hydoxyl and sulphanyl ions, OH+ and SH+. Hyperfine resolved rate coefficients are deduced using the infinite-order-sudden approximation. The propensity rule ΔF = Δj = ΔN = ±1 is observed, as is expected for cations with a large dipole moment. A model for OH+ excitation in the Orion Bar photon-dominated region is presented which nicely reproduces Herschel observations for an electron fraction xe = 10-4 and an OH+ column density of 3 × 1013 cm-2. Electron-impact electronic excitation cross-sections and rate coefficients for the ions are also presented.

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.

Molecular hyperfine fields in organic magnetoresistance devices

NASA Astrophysics Data System (ADS)

Giro, Ronaldo; Rosselli, Flávia P.; dos Santos Carvalho, Rafael; Capaz, Rodrigo B.; Cremona, Marco; Achete, Carlos A.

2013-03-01

We calculate molecular hyperfine fields in organic magnetoresistance (OMAR) devices using ab initio calculations. To do so, we establish a protocol for the accurate determination of the average hyperfine field Bhf and apply it to selected molecular ions: NPB, TPD, and Alq3. Then, we make devices with precisely the same molecules and perform measurements of the OMAR effect, in order to address the role of hole-transport layer in the characteristic magnetic field B0 of OMAR. Contrary to common belief, we find that molecular hyperfine fields are not only caused by hydrogen nuclei. We also find that dipolar contributions to the hyperfine fields can be comparable to the Fermi contact contributions. However, such contributions are restricted to nuclei located in the same molecular ion as the charge carrier (intramolecular), as extramolecular contributions are negligible.

First principles study of the ground state properties of Si, Ga, and Ge doped Fe50Al50

NASA Astrophysics Data System (ADS)

Pérez, Carlos Ariel Samudio; dos Santos, Antonio Vanderlei

2018-06-01

The first principles calculation of the structural, electronic and associated properties of the Fe50Al50 alloy (B2 phase) doped by s-p elements (Im = Si, Ga, and Ge) are performed as a function of the atomic concentration on the basis of the Full Potential Linear Augmented Plane Wave (FP-LAPW) method as implemented in the WIEN2k code. The Al substitution by Im (Si and Ge) atoms (principally at a concentration of 6.25 at%) induces a pronounced redistribution of the electronic charge leading to a strong Fe-Im interaction with covalent bonding character. At the same time, decrease the lattice volume (V) while increase the bulk modulus (B). For the alloys containing Ga, the Fe-Ga interaction is also observed but the V and B of the alloy are very near to that of pure Fe-Al alloy. The magnetic moment and hyperfine parameters observed at the lattice sites of studied alloys also show variations, they increase or decrease in relation to that in Fe50Al50 according to the Im that substitutes Al.

Ultrafast Pulse Sequencing for Fast Projective Measurements of Atomic Hyperfine Qubits

NASA Astrophysics Data System (ADS)

Ip, Michael; Ransford, Anthony; Campbell, Wesley

2015-05-01

Projective readout of quantum information stored in atomic hyperfine structure typically uses state-dependent CW laser-induced fluorescence. This method requires an often sophisticated imaging system to spatially filter out the background CW laser light. We present an alternative approach that instead uses simple pulse sequences from a mode-locked laser to affect the same state-dependent excitations in less than 1 ns. The resulting atomic fluorescence occurs in the dark, allowing the placement of non-imaging detectors right next to the atom to improve the qubit state detection efficiency and speed. We also discuss methods of Doppler cooling with mode-locked lasers for trapped ions, where the creation of the necessary UV light is often difficult with CW lasers.

Copper ESEEM and HYSCORE through ultra-wideband chirp EPR spectroscopy

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

Segawa, Takuya F.; Doll, Andrin; Pribitzer, Stephan

2015-07-28

The main limitation of pulse electron paramagnetic resonance (EPR) spectroscopy is its narrow excitation bandwidth. Ultra-wideband (UWB) excitation with frequency-swept chirp pulses over several hundreds of megahertz overcomes this drawback. This allows to excite electron spin echo envelope modulation (ESEEM) from paramagnetic copper centers in crystals, whereas up to now, only ESEEM of ligand nuclei like protons or nitrogens at lower frequencies could be detected. ESEEM spectra are recorded as two-dimensional correlation experiments, since the full digitization of the electron spin echo provides an additional Fourier transform EPR dimension. Thus, UWB hyperfine-sublevel correlation experiments generate a novel three-dimensional EPR-correlated nuclearmore » modulation spectrum.« less

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

Samskog, P.; Kispert, L.D.; Lund, A.

Three different radicals were identified by EPR in x-ray irradiated single crystals of trehalose at 3 K. The species are the trapped electron, a hydroxy alkyl radical, and an alkoxy radical. The electron is trapped in an intermolecular site formed by two hydroxyl groups, one on the carbohydrate and the other on a water molecule as evidenced by the anisotropic proton hyperfine couplings. A geometric model for the trapping site is presented. The trapped electron decays by cleavage of an OH bond and the liberated hydrogen atom abstracts another hydrogen atom from an adjacent carbon atom forming a hydroxy alkylmore » radical. The site of the alkoxy radical has been identified. The primary reaction mechanism is discussed.« less

Effect of Charge Localization on the Effective Hyperfine Interaction in Organic Semiconducting Polymers

NASA Astrophysics Data System (ADS)

Geng, Rugang; Subedi, Ram C.; Luong, Hoang M.; Pham, Minh T.; Huang, Weichuan; Li, Xiaoguang; Hong, Kunlun; Shao, Ming; Xiao, Kai; Hornak, Lawrence A.; Nguyen, Tho D.

2018-02-01

Hyperfine interaction (HFI), originating from the coupling between spins of charge carriers and nuclei, has been demonstrated to strongly influence the spin dynamics of localized charges in organic semiconductors. Nevertheless, the role of charge localization on the HFI strength in organic thin films has not yet been experimentally investigated. In this study, the statistical relation hypothesis that the effective HFI of holes in regioregular poly(3-hexylthiophene) (P3HT) is proportional to 1 /N0.5 has been examined, where N is the number of the random nuclear spins within the envelope of the hole wave function. First, by studying magnetoconductance in hole-only devices made by isotope-labeled P3HT we verify that HFI is indeed the dominant spin interaction in P3HT. Second, assuming that holes delocalize fully over the P3HT polycrystalline domain, the strength of HFI is experimentally demonstrated to be proportional to 1 /N0.52 in excellent agreement with the statistical relation. Third, the HFI of electrons in P3HT is about 3 times stronger than that of holes due to the stronger localization of the electrons. Finally, the effective HFI in organic light emitting diodes is found to be a superposition of effective electron and hole HFI. Such a statistical relation may be generally applied to other semiconducting polymers. This Letter may provide great benefits for organic optoelectronics, chemical reaction kinetics, and magnetoreception in biology.

Effect of Charge Localization on the Effective Hyperfine Interaction in Organic Semiconducting Polymers.

PubMed

Geng, Rugang; Subedi, Ram C; Luong, Hoang M; Pham, Minh T; Huang, Weichuan; Li, Xiaoguang; Hong, Kunlun; Shao, Ming; Xiao, Kai; Hornak, Lawrence A; Nguyen, Tho D

2018-02-23

Hyperfine interaction (HFI), originating from the coupling between spins of charge carriers and nuclei, has been demonstrated to strongly influence the spin dynamics of localized charges in organic semiconductors. Nevertheless, the role of charge localization on the HFI strength in organic thin films has not yet been experimentally investigated. In this study, the statistical relation hypothesis that the effective HFI of holes in regioregular poly(3-hexylthiophene) (P3HT) is proportional to 1/N^{0.5} has been examined, where N is the number of the random nuclear spins within the envelope of the hole wave function. First, by studying magnetoconductance in hole-only devices made by isotope-labeled P3HT we verify that HFI is indeed the dominant spin interaction in P3HT. Second, assuming that holes delocalize fully over the P3HT polycrystalline domain, the strength of HFI is experimentally demonstrated to be proportional to 1/N^{0.52} in excellent agreement with the statistical relation. Third, the HFI of electrons in P3HT is about 3 times stronger than that of holes due to the stronger localization of the electrons. Finally, the effective HFI in organic light emitting diodes is found to be a superposition of effective electron and hole HFI. Such a statistical relation may be generally applied to other semiconducting polymers. This Letter may provide great benefits for organic optoelectronics, chemical reaction kinetics, and magnetoreception in biology.

Chirp echo Fourier transform EPR-detected NMR.

PubMed

Wili, Nino; Jeschke, Gunnar

2018-04-01

A new ultra-wide band (UWB) pulse EPR method is introduced for observing all nuclear frequencies of a paramagnetic center in a single shot. It is based on burning spectral holes with a high turning angle (HTA) pulse that excites forbidden transitions and subsequent detection of the hole pattern by a chirp echo. We term this method Chirp Echo Epr SpectroscopY (CHEESY)-detected NMR. The approach is a revival of FT EPR-detected NMR. It yields similar spectra and the same type of information as electron-electron double resonance (ELDOR)-detected NMR, but with a multiplex advantage. We apply CHEESY-detected NMR in Q band to nitroxides and correlate the hyperfine spectrum to the EPR spectrum by varying the frequency of the HTA pulse. Furthermore, a selective π pulse before the HTA pulse allows for detecting hyperfine sublevel correlations between transitions of one nucleus and for elucidating the coupling regime, the same information as revealed by the HYSCORE experiment. This is demonstrated on hexaaquamanganese(II). We expect that CHEESY-detected NMR is generally applicable to disordered systems and that our results further motivate the development of EPR spectrometers capable of coherent UWB excitation and detection, especially at higher fields and frequencies. Copyright © 2018 The Author(s). Published by Elsevier Inc. All rights reserved.

Measurement of the spin temperature of optically cooled nuclei and GaAs hyperfine constants in GaAs/AlGaAs quantum dots

NASA Astrophysics Data System (ADS)

Chekhovich, E. A.; Ulhaq, A.; Zallo, E.; Ding, F.; Schmidt, O. G.; Skolnick, M. S.

2017-10-01

Deep cooling of electron and nuclear spins is equivalent to achieving polarization degrees close to 100% and is a key requirement in solid-state quantum information technologies. While polarization of individual nuclear spins in diamond and SiC (ref. ) reaches 99% and beyond, it has been limited to 50-65% for the nuclei in quantum dots. Theoretical models have attributed this limit to formation of coherent `dark' nuclear spin states but experimental verification is lacking, especially due to the poor accuracy of polarization degree measurements. Here we measure the nuclear polarization in GaAs/AlGaAs quantum dots with high accuracy using a new approach enabled by manipulation of the nuclear spin states with radiofrequency pulses. Polarizations up to 80% are observed--the highest reported so far for optical cooling in quantum dots. This value is still not limited by nuclear coherence effects. Instead we find that optically cooled nuclei are well described within a classical spin temperature framework. Our findings unlock a route for further progress towards quantum dot electron spin qubits where deep cooling of the mesoscopic nuclear spin ensemble is used to achieve long qubit coherence. Moreover, GaAs hyperfine material constants are measured here experimentally for the first time.

Bandwidth-limited control and ringdown suppression in high-Q resonators.

PubMed

Borneman, Troy W; Cory, David G

2012-12-01

We describe how the transient behavior of a tuned and matched resonator circuit and a ringdown suppression pulse may be integrated into an optimal control theory (OCT) pulse-design algorithm to derive control sequences with limited ringdown that perform a desired quantum operation in the presence of resonator distortions of the ideal waveform. Inclusion of ringdown suppression in numerical pulse optimizations significantly reduces spectrometer deadtime when using high quality factor (high-Q) resonators, leading to increased signal-to-noise ratio (SNR) and sensitivity of inductive measurements. To demonstrate the method, we experimentally measure the free-induction decay of an inhomogeneously broadened solid-state free radical spin system at high Q. The measurement is enabled by using a numerically optimized bandwidth-limited OCT pulse, including ringdown suppression, robust to variations in static and microwave field strengths. We also discuss the applications of pulse design in high-Q resonators to universal control of anisotropic-hyperfine coupled electron-nuclear spin systems via electron-only modulation even when the bandwidth of the resonator is significantly smaller than the hyperfine coupling strength. These results demonstrate how limitations imposed by linear response theory may be vastly exceeded when using a sufficiently accurate system model to optimize pulses of high complexity. Copyright © 2012 Elsevier Inc. All rights reserved.

Magnetic correlations in La(2-x)Sr(x)CuO4 from NQR relaxation and specific heat

NASA Technical Reports Server (NTRS)

Borsa, F.; Rigamonti, A.

1990-01-01

La-139 and Cu-63 Nuclear Quadrupole Resonance (NQR) relaxation measurements in La(2-x)Sr(x)CuO4 for O = to or less than 0.3 and in the temperature range 1.6 + 450 K are analyzed in terms of Cu(++) magnetic correlations and dynamics. It is described how the magnetic correlations that would result from Cu-Cu exchange are reduced by mobile charge defects related to x-doping. A comprehensive picture is given which explains satisfactorily the x and T dependence of the correlation time, of the correlation length and of the Neel temperature T(sub n)(x) as well as being consistent with known electrical resistivity and magnetic susceptibility measurements. It is discussed how, in the superconducting samples, the mobile defects also cause the decrease, for T yields T(sub c)(+) of the hyperfine Cu electron-nucleus effective interaction, leading to the coexistence of quasi-localized, reduced magnetic moments from 3d Cu electrons and mobile oxygen p-hole carriers. The temperature dependence of the effective hyperfine field around the superconducting transition yields an activation energy which could be related to the pairing energy. New specific heat measurements are also presented and discussed in terms of the above picture.

Enzymatic mechanisms of biological magnetic sensitivity.

PubMed

Letuta, Ulyana G; Berdinskiy, Vitaly L; Udagawa, Chikako; Tanimoto, Yoshifumi

2017-10-01

Primary biological magnetoreceptors in living organisms is one of the main research problems in magnetobiology. Intracellular enzymatic reactions accompanied by electron transfer have been shown to be receptors of magnetic fields, and spin-dependent ion-radical processes can be a universal mechanism of biological magnetosensitivity. Magnetic interactions in intermediate ion-radical pairs, such as Zeeman and hyperfine (HFI) interactions, in accordance with proposed strict quantum mechanical theory, can determine magnetic-field dependencies of reactions that produce biologically important molecules needed for cell growth. Hyperfine interactions of electrons with nuclear magnetic moments of magnetic isotopes can explain the most important part of biomagnetic sensitivities in a weak magnetic field comparable to the Earth's magnetic field. The theoretical results mean that magnetic-field dependencies of enzymatic reaction rates in a weak magnetic field that can be independent of HFI constant a, if H < a, and are determined by the rate constant of chemical transformations in the enzyme active site. Both Zeeman and HFI interactions predict strong magnetic-field dependence in weak magnetic fields and magnetic-field independence of enzymatic reaction rate constants in strong magnetic fields. The theoretical results can explain the magnetic sensitivity of E. coli cell and demonstrate that intracellular enzymatic reactions are primary magnetoreceptors in living organisms. Bioelectromagnetics. 38:511-521, 2017. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Laboratory detection of the rotational-tunnelling spectrum of the hydroxymethyl radical, CH2OH

NASA Astrophysics Data System (ADS)

Bermudez, C.; Bailleux, S.; Cernicharo, J.

2017-02-01

Context. Of the two structural isomers of CH3O, methoxy is the only radical whose astronomical detection has been reported through the observation of several rotational lines at 2 and 3 mm wavelengths. Although the hydroxymethyl radical, CH2OH, is known to be thermodynamically the most stable (by 3300 cm-1), it has so far eluded rotational spectroscopy presumably because of its high chemical reactivity. Aims: Recent high-resolution ( 10 MHz) sub-Doppler rovibrationally resolved infrared spectra of CH2OH (symmetric CH stretching a-type band) provided accurate ground vibrational state rotational constants, thus reviving the quest for its millimeter-wave spectrum in laboratory and subsequently in space. Methods: The search and assignment of the rotational spectrum of this fundamental species were guided by our quantum chemical calculations and by using rotational constants derived from high-resolution IR data. The hydroxymethyl radical was produced by hydrogen abstraction from methanol by atomic chlorine. Results: Ninety-six b-type rotational transitions between the v = 0 and v = 1 tunnelling sublevels involving 25 fine-structure components of Q branches (with Ka = 1 ← 0) and 4 fine-structure components of R branches (assigned to Ka = 0 ← 1) were measured below 402 GHz. Hyperfine structure alternations due to the two identical methylenic hydrogens were observed and analysed based on the symmetry and parity of the rotational levels. A global fit including infrared and millimeter-wave lines has been conducted using Pickett's reduced axis system Hamiltonian. The recorded transitions (odd ΔKa) did not allow us to evaluate the Coriolis tunnelling interaction term. The comparison of the experimentally determined constants for both tunnelling levels with their computed values secures the long-awaited first detection of the rotational-tunnelling spectrum of this radical. In particular, a tunnelling rate of 139.73 ± 0.10 MHz (4.6609(32) × 10-3 cm-1) was obtained along with the rotational constants, electron spin-rotation interaction parameters and several hyperfine coupling terms. Conclusions: The laboratory characterization of CH2OH by millimeter-wave spectroscopy now offers the possibility for its astronomical detection for the first time.

Using Hyperfine Structure Limits to Characterize the Formaldehyde Maser in G32.74-0.07

NASA Astrophysics Data System (ADS)

Araya, Esteban; Nazmus Sakib, Md; Olmi, Luca; Hofner, Peter; Kurtz, Stan; Hoffman, Ian M.; Linz, Hendrik

2018-06-01

Formaldehyde (H2CO) masers are a rare variety of astrophysical masers, but they have the virtue of exclusively tracing the interiors of high-mass star forming regions. We report observations conducted with the 305m Arecibo Telescope and the Karl G. Jansky Very Large Array (VLA) of the 6 cm H2CO maser in the region of high-mass star formation G32.74-0.07. This maser is among the narrowest H2CO masers known, and thus it is an excellent candidate to study the excitation of the hyperfine components of the transition. The Arecibo and VLA results are consistent, the maser flux density observed with Arecibo is recovered in the VLA image within the rms noise of the spectra, and the fitted line widths of the two observations agree to within formal errors. Our high signal-to-noise (~7 mJy rms) and high spectral resolution (0.05 km/s) observations allow us to set strong limits on the hyperfine structure of the line. The line profile is consistent with unsaturated emission, with a maser gain of approximately 3, and an amplified background radio continuum of ~1 mJy. VLA observations confirm the presence of a continuum source at the location of the maser. The continuum source is characterized by a spectral index of +0.9 at 5 GHz, which is indicative of thermal Bremsstrahlung in the optically thick/thin transition.

Study of nanostructural organization of ionic liquids by electron paramagnetic resonance spectroscopy.

PubMed

Merunka, Dalibor; Peric, Mirna; Peric, Miroslav

2015-02-19

The X-band electron paramagnetic resonance spectroscopy (EPR) of a stable, spherical nitroxide spin probe, perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (pDTO) has been used to study the nanostructural organization of a series of 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids (ILs) with alkyl chain lengths from two to eight carbons. By employing nonlinear least-squares fitting of the EPR spectra, we have obtained values of the rotational correlation time and hyperfine coupling splitting of pDTO to high precision. The rotational correlation time of pDTO in ILs and squalane, a viscous alkane, can be fit very well to a power law functionality with a singular temperature, which often describes a number of physical quantities measured in supercooled liquids. The viscosity of the ILs and squalane, taken from the literature, can also be fit to the same power law expression, which means that the rotational correlation times and the ionic liquid viscosities have similar functional dependence on temperature. The apparent activation energy of both the rotational correlation time of pDTO and the viscous flow of ILs and squalane increases with decreasing temperature; in other words, they exhibit strong non-Arrhenius behavior. The rotational correlation time of pDTO as a function of η/T, where η is the shear viscosity and T is the temperature, is well described by the Stokes-Einstein-Debye (SED) law, while the hydrodynamic probe radii are solvent dependent and are smaller than the geometric radius of the probe. The temperature dependence of hyperfine coupling splitting is the same in all four ionic liquids. The value of the hyperfine coupling splitting starts decreasing with increasing alkyl chain length in the ionic liquids in which the number of carbons in the alkyl chain is greater than four. This decrease together with the decrease in the hydrodynamic radius of the probe indicates a possible existence of nonpolar nanodomains.

A partitioned correlation function interaction approach for describing electron correlation in atoms

NASA Astrophysics Data System (ADS)

Verdebout, S.; Rynkun, P.; Jönsson, P.; Gaigalas, G.; Froese Fischer, C.; Godefroid, M.

2013-04-01

The traditional multiconfiguration Hartree-Fock (MCHF) and configuration interaction (CI) methods are based on a single orthonormal orbital basis. For atoms with many closed core shells, or complicated shell structures, a large orbital basis is needed to saturate the different electron correlation effects such as valence, core-valence and correlation within the core shells. The large orbital basis leads to massive configuration state function (CSF) expansions that are difficult to handle, even on large computer systems. We show that it is possible to relax the orthonormality restriction on the orbital basis and break down the originally very large calculations into a series of smaller calculations that can be run in parallel. Each calculation determines a partitioned correlation function (PCF) that accounts for a specific correlation effect. The PCFs are built on optimally localized orbital sets and are added to a zero-order multireference (MR) function to form a total wave function. The expansion coefficients of the PCFs are determined from a low dimensional generalized eigenvalue problem. The interaction and overlap matrices are computed using a biorthonormal transformation technique (Verdebout et al 2010 J. Phys. B: At. Mol. Phys. 43 074017). The new method, called partitioned correlation function interaction (PCFI), converges rapidly with respect to the orbital basis and gives total energies that are lower than the ones from ordinary MCHF and CI calculations. The PCFI method is also very flexible when it comes to targeting different electron correlation effects. Focusing our attention on neutral lithium, we show that by dedicating a PCF to the single excitations from the core, spin- and orbital-polarization effects can be captured very efficiently, leading to highly improved convergence patterns for hyperfine parameters compared with MCHF calculations based on a single orthogonal radial orbital basis. By collecting separately optimized PCFs to correct the MR function, the variational degrees of freedom in the relative mixing coefficients of the CSFs building the PCFs are inhibited. The constraints on the mixing coefficients lead to small off-sets in computed properties such as hyperfine structure, isotope shift and transition rates, with respect to the correct values. By (partially) deconstraining the mixing coefficients one converges to the correct limits and keeps the tremendous advantage of improved convergence rates that comes from the use of several orbital sets. Reducing ultimately each PCF to a single CSF with its own orbital basis leads to a non-orthogonal CI approach. Various perspectives of the new method are given.

Free Radical Metabolism of Methyleugenol and Related Compounds

PubMed Central

2015-01-01

Methyleugenol, the methyl ether of eugenol, both of which are flavorant constituents of spices, has been listed by the National Toxicology Program’s Report on Carcinogens as reasonably anticipated to be a human carcinogen. This finding is based on the observation of increased incidence of malignant tumors at multiple tissue sites in experimental animals of different species. By contrast, eugenol is not listed. In this study, we show that both methyleugenol and eugenol readily undergo peroxidative metabolism in vitro to form free radicals with large hyperfine interactions of the methylene allylic hydrogen atoms. These large hyperfine splittings indicate large electron densities adjacent to those hydrogen atoms. Methyleugenol undergoes autoxidation such that the commercial product contains 10–30 mg/L hydroperoxide and is capable of activating peroxidases without the presence of added hydrogen peroxide. Additionally, the hydroperoxide is not a good substrate for catalase, which demonstrates that these antioxidant defenses will not be effective in protecting against methyleugenol exposure. PMID:24564854

Transport-related triplet states and hyperfine couplings in organic tandem solar cells probed by pulsed electrically detected magnetic resonance spectroscopy

NASA Astrophysics Data System (ADS)

Kraffert, Felix; Bahro, Daniel; Meier, Christoph; Denne, Maximilian; Colsmann, Alexander; Behrends, Jan

2017-09-01

Tandem solar cells constitute the most successful organic photovoltaic devices with power conversion efficiencies comparable to thin-film silicon solar cells. Especially their high open-circuit voltage - only achievable by a well-adjusted layer stacking - leads to their high efficiencies. Nevertheless, the microscopic processes causing the lossless recombination of charge carriers within the recombination zone are not well understood yet. We show that advanced pulsed electrically detected magnetic resonance techniques such as electrically detected (ED)-Rabi nutation measurements and electrically detected hyperfine sublevel correlation (ED-HYSCORE) spectroscopy help to understand the role of triplet excitons in these microscopic processes. We investigate fully working miniaturised organic tandem solar cells and detect current-influencing doublet states in different layers as well as triplet excitons located on the fullerene-based acceptor. We apply ED-HYSCORE in order to study the nuclear spin environment of the relevant electron/hole spins and detect a significant amount of the low abundant 13C nuclei coupled to the observer spins.

Experimental and theoretical study of Co sorption in clay montmorillonites

NASA Astrophysics Data System (ADS)

Gil Rebaza, A. V.; Montes, M. L.; Taylor, M. A.; Errico, L. A.; Alonso, R. E.

2018-03-01

Montmorillonite (MMT) clays are 2:1 layered structures which in natural state may allocate different hydrated cations such as M-nH2O (M = Na, Ca, Fe, etc) in its interlayer space. Depending on the capability for ion sorption, these materials are interesting for environmental remediation. In this work we experimentally study the Co sorption in a natural Na-MMT using UV-visible spectrometry and XRD on semi-oriented samples, and then analyze the sorption ability of this clay by means of ab initio calculation performed on pristine MMT. The structural properties of Na-MMT and Co-adsorbed MMT, and the hyperfine parameters at different atomic sites were analyzed and compared with the experimental ones for the first, and for the case of the hyperfine parameters, presented for the first time for the last. The theoretical predictions based on total energy considerations confirm that Co incorporation replacing Na is energetically favorable. Also, the basal spacing d001 experimentally obtained is well reproduced.

The optical depth of the 158 micron forbidden C-12 II line - Detection of the F = 1 - 0 forbidden C-13 II hyperfine-structure component. [in Orion nebula

NASA Technical Reports Server (NTRS)

Stacey, G. J.; Townes, C. H.; Geis, N.; Madden, S. C.; Herrmann, F.; Genzel, R.; Poglitsch, A.; Jackson, J. M.

1991-01-01

The detection of the F = 1 - 0 hyperfine component of the 158-micron forbidden C-13 II fine-structure line in the interstellar medium is reported. A 12-point intensity map was obtained of the forbidden C-13 distribution over the inner 190-arcsec (R.A.) X 190-arcsec (decl.) regions of the Orion Nebula using an imaging Fabry-Perot interferometer. The forbidden C-12 II/C-13 II line intensity ratio varies significantly over the region mapped. It is highest (86 +/-0) in the core of the Orion H II region, and significantly lower (62 +/-7) in the outer regions of the map, reflecting higher optical depth in the forbidden C-12 II line here. It is suggested that this enhanced optical depth is the result of limb brightening of the optically thin forbidden C-13 II line at the edges of the bowl-shaped H II region blister.

Calculation of spin-densities within the context of density functional theory. The crucial role of the correlation functional

NASA Astrophysics Data System (ADS)

Filatov, Michael; Cremer, Dieter

2005-09-01

It is demonstrated that the LYP correlation functional is not suited to be used for the calculation of electron spin resonance hyperfine structure (HFS) constants, nuclear magnetic resonance spin-spin coupling constants, magnetic, shieldings and other properties that require a balanced account of opposite- and equal-spin correlation, especially in the core region. In the case of the HFS constants of alkali atoms, LYP exaggerates opposite-spin correlation effects thus invoking too strong in-out correlation effects, an exaggerated spin-polarization pattern in the core shells of the atoms, and, consequently, too large HFS constants. Any correlation functional that provides a balanced account of opposite- and equal-spin correlation leads to improved HFS constants, which is proven by comparing results obtained with the LYP and the PW91 correlation functional. It is suggested that specific response properties are calculated with the PW91 rather than the LYP correlation functional.

Spin-dependent recombination probed through the dielectric polarizability

PubMed Central

Bayliss, Sam L.; Greenham, Neil C.; Friend, Richard H.; Bouchiat, Hélène; Chepelianskii, Alexei D

2015-01-01

Despite residing in an energetically and structurally disordered landscape, the spin degree of freedom remains a robust quantity in organic semiconductor materials due to the weak coupling of spin and orbital states. This enforces spin-selectivity in recombination processes which plays a crucial role in optoelectronic devices, for example, in the spin-dependent recombination of weakly bound electron-hole pairs, or charge-transfer states, which form in a photovoltaic blend. Here, we implement a detection scheme to probe the spin-selective recombination of these states through changes in their dielectric polarizability under magnetic resonance. Using this technique, we access a regime in which the usual mixing of spin-singlet and spin-triplet states due to hyperfine fields is suppressed by microwave driving. We present a quantitative model for this behaviour which allows us to estimate the spin-dependent recombination rate, and draw parallels with the Majorana–Brossel resonances observed in atomic physics experiments. PMID:26439933

Incommensurate to commensurate antiferromagnetism in CeRhAl 4 Si 2 : An Al 27 NMR study

DOE PAGES

Sakai, Hironori; Hattori, T.; Tokunaga, Y.; ...

2016-01-04

27Al nuclear magnetic resonance (NMR) experiments have been performed on a single crystal of CeRhAl 4Si 2, which is an antiferromagnetic Kondo-lattice compound with successive antiferromagnetic transitions of T N1 = 14 K and T N2 = 9 K at zero external field. In the paramagnetic state, the Knight shifts, quadrupolar frequency, and asymmetric parameter of electrical field gradient on the Al sites have been determined, which have local orthorhombic symmetry. The transferred hyperfine coupling constants are also determined. Here, analysis of the NMR spectra indicates that a commensurate antiferromagnetic structure exists below T N2, but an incommensurate modulation ofmore » antiferromagnetic moments is present in the antiferromagnetic state between T N1 and T N2. The spin-lattice relaxation rate suggests that the 4f electrons behave as local moments at temperatures above T N1.« less

THEORETICAL RESEARCH OF THE OPTICAL SPECTRA AND EPR PARAMETERS FOR Cs2NaYCl6:Dy3+ CRYSTAL

NASA Astrophysics Data System (ADS)

Dong, Hui-Ning; Dong, Meng-Ran; Li, Jin-Jin; Li, Deng-Feng; Zhang, Yi

2013-09-01

The calculated EPR parameters are in reasonable agreement with the observed values. The important material Cs2NaYCl6 doped with rare earth ions have received much attention because of its excellent optical and magnetic properties. Based on the superposition model, in this paper the crystal field energy levels, the electron paramagnetic resonance parameters g factors of Dy3+ and hyperfine structure constants of 161Dy3+ and 163Dy3+ isotopes in Cs2NaYCl6 crystal are studied by diagonalizing the 42 × 42 energy matrix. In the calculations, the contributions of various admixtures and interactions such as the J-mixing, the mixtures among the states with the same J-value, and the covalence are all considered. The calculated results are in reasonable agreement with the observed values. The results are discussed.

Effect of synthesis methods with different annealing temperatures on micro structure, cations distribution and magnetic properties of nano-nickel ferrite

NASA Astrophysics Data System (ADS)

El-Sayed, Karimat; Mohamed, Mohamed Bakr; Hamdy, Sh.; Ata-Allah, S. S.

2017-02-01

Nano-crystalline NiFe2O4 was synthesized by citrate and sol-gel methods at different annealing temperatures and the results were compared with a bulk sample prepared by ceramic method. The effect of methods of preparation and different annealing temperatures on the crystallize size, strain, bond lengths, bond angles, cations distribution and degree of inversions were investigated by X-ray powder diffraction, high resolution transmission electron microscope, Mössbauer effect spectrometer and vibrating sample magnetometer. The cations distributions were determined at both octahedral and tetrahedral sites using both Mössbauer effect spectroscopy and a modified Bertaut method using Rietveld method. The Mössbauer effect spectra showed a regular decrease in the hyperfine field with decreasing particle size. Saturation magnetization and coercivity are found to be affected by the particle size and the cations distribution.

The ferromagnetic monolayer Fe(110) on W(110)

NASA Astrophysics Data System (ADS)

Gradmann, U.; Liu, G.; Elmers, H. J.; Przybylski, M.

1990-07-01

Ferromagnetic order in the pseudomorphic monolayer Fe(110) on W(110) was analyzed experimentally using Conversion Electron Mössbauer Spectroscopy (CEMS) and Torsion Oscillation Magnetometry (TOM). The monolayer is thermodynamically stable, crystallizes to large monolayer patches at elevated temperatures and therefore forms an excellent approximation to the ideal monolayer structure. It is ferromagnetic below a Curie-temperature T c,mono, which is given by (282±3) K for the Ag-coated layer, (290±10) K for coating by Cu, Ag or Au and ≈210 K for the free monolayer. For the Ag-coated monolayer, ground state hyperfine field B hf (0)=(11.9±0.3) T and magnetic moment per atom μ=2.53 μB could be determined, in fair agreement with theoretical predictions. Unusual properties of the phase transition are detected by the combination of both experimental techniques. Strong magnetic anisotropies, which are essential for ferromagnetic order, are determined by CEMS.

Fourier transform microwave spectroscopy of the SiCl+ ion

NASA Astrophysics Data System (ADS)

Tanaka, Keiichi; Harada, Kensuke; Cabezas, Carlos; Endo, Yasuki

2018-03-01

Fourier transform microwave spectra for the J = 1 ← 0 and 2 ← 1 rotational transitions of the SiCl+ ion were observed for two isotopologues (35 Cl and 37 Cl) in the ground and the first excited vibrational states of the ground 1Σ+ electronic state. Thanks to the high resolution of the FTMW spectrometer, hyperfine structures due to the quadrupole moment of the chlorine nucleus and the nuclear spin-rotation interaction were fully resolved. The observed FTMW spectra were combined with previously reported MMW and diode laser spectra in an analysis to determine the mass-independent Dunham coefficients Uk,l as well as a mass scaling parameter Δ01Cl = - 0.856 (30) . The equilibrium bond length of SiCl+ determined is re = 1.9439729 (10) Å and the nuclear quadrupole coupling constant of Si35 Cl+ is eQqe = - 11.8788 (23) MHz.

The Pure Rotational Spectrum of KO

NASA Astrophysics Data System (ADS)

Burton, Mark; Russ, Benjamin; Sheridan, Phillip M.; Bucchino, Matthew; Ziurys, Lucy M.

2017-06-01

The pure rotational spectrum of potassium monoxide (KO) has been recorded using millimeter-wave direct absorption spectroscopy. KO was synthesized by the reaction of potassium vapor, produced in a Broida-type oven, with nitrous oxide. No DC discharge was necessary. Eleven rotational transitions belonging to the ^{2}Π_{3/2} spin-orbit component have been measured and have been fit successfully to a case (c) Hamiltonian. Rotational and lambda-doubling constants for this spin-orbit component have been determined. It has been suggested that the ground electronic state of KO is either ^{2}Π (as for LiO and NaO) or ^{2}Σ (as for RbO and CsO), both of which lie close in energy. Recent computational studies favor a ^{2}Σ ground state. Further measurements of the rotational transitions of the ^{2}Π_{1/2} spin-orbit component and the ^{2}Σ state are currently in progress, as well as the potassium hyperfine structure.

Magnetic properties of single crystal alpha-benzoin oxime: An EPR study

NASA Astrophysics Data System (ADS)

Sayin, Ulku; Dereli, Ömer; Türkkan, Ercan; Ozmen, Ayhan

2012-02-01

The electron paramagnetic resonance (EPR) spectra of gamma irradiated single crystals of alpha-benzoinoxime (ABO) have been examined between 120 and 440 K. Considering the dependence on temperature and the orientation of the spectra of single crystals in the magnetic field, we identified two different radicals formed in irradiated ABO single crystals. To theoretically determine the types of radicals, the most stable structure of ABO was obtained by molecular mechanic and B3LYP/6-31G(d,p) calculations. Four possible radicals were modeled and EPR parameters were calculated for the modeled radicals using the B3LYP method and the TZVP basis set. Calculated values of two modeled radicals were in strong agreement with experimental EPR parameters determined from the spectra. Additional simulated spectra of the modeled radicals, where calculated hyperfine coupling constants were used as starting points for simulations, were well matched with experimental spectra.

Monoanionic molybdenum and tungsten tris(dithiolene) complexes: a multifrequency EPR study.

PubMed

Sproules, Stephen; Banerjee, Priyabrata; Weyhermüller, Thomas; Yan, Yong; Donahue, James P; Wieghardt, Karl

2011-08-01

Numerous Mo and W tris(dithiolene) complexes in varying redox states have been prepared and representative examples characterized crystallographically: [M(S(2)C(2)R(2))(3)](z) [M = Mo, R = Ph, z = 0 (1) or 1- (2); M = W, R = Ph, z = 0 (4) or 1- (5); R = CN, z = 2-, M = Mo (3) or W (6)]. Changes in dithiolene C-S and C-C bond lengths for 1 versus 2 and 4 versus 5 are indicative of ligand reduction. Trigonal twist angles (Θ) and dithiolene fold angles (α) increase and decrease, respectively, for 2 versus 1, 5 versus 4. Cyclic voltammetry reveals generally two reversible couples corresponding to 0/1- and 1-/2- reductions. The electronic structures of monoanionic molybdenum tris(dithiolene) complexes have been analyzed by multifrequency (S-, X-, Q-band) EPR spectroscopy. Spin-Hamiltonian parameters afforded by spectral simulation for each complex demonstrate the existence of two distinctive electronic structure types. The first is [Mo(IV)((A)L(3)(5-•))](1-) ((A)L = olefinic dithiolene, type A), which has the unpaired electron restricted to the tris(dithiolene) unit and is characterized by isotropic g-values and small molybdenum superhyperfine coupling. The second is formulated as [Mo(V)((B)L(3)(6-))](1-) ((B)L = aromatic dithiolene, type B) with spectra distinguished by a prominent g-anisotropy and hyperfine coupling consistent with the (d(z(2)))(1) paramagnet. The electronic structure disparity is also manifested in their electronic absorption spectra. The compound [W(bdt)(3)](1-) exhibits spin-Hamiltonian parameters similar to those of [Mo(bdt)(3)](1-) and thus is formulated as [W(V)((B)L(3)(6-))](1-). The EPR spectra of [W((A)L(3))](1-) display spin-Hamiltonian parameters that suggest their electronic structure is best represented by two resonance forms {[W(IV)((A)L(3)(5-•))](1-) ↔ [W(V)((A)L(3)(6-))](1-)}. The contrast with the corresponding [Mo(IV)((A)L(3)(5-•))](1-) complexes highlights tungsten's preference for higher oxidation states. © 2011 American Chemical Society

Evidence for changes in the nucleotide conformation in the active site of H(+)-ATPase as determined by pulsed EPR spectroscopy.

PubMed

Schneider, B; Sigalat, C; Amano, T; Zimmermann, J L

2000-12-19

The conformation of di- and triphosphate nucleosides in the active site of ATPsynthase (H(+)-ATPase) from thermophilic Bacillus PS3 (TF1) and their interaction with Mg(2+)/Mn(2+) cations have been investigated using EPR, ESEEM, and HYSCORE spectroscopies. For a ternary complex formed by a stoichiometric mixture of TF1, Mn(2+), and ADP, the ESEEM and HYSCORE data reveal a (31)P hyperfine interaction with Mn(2+) (|A((31)P)| approximately 5.20 MHz), significantly larger than that measured for the complex formed by Mn(2+) and ADP in solution (|A((31)P)| approximately 4.50 MHz). The Q-band EPR spectrum of the Mn.TF1.ADP complex indicates that the Mn(2+) binds in a slightly distorted environment with |D| approximately 180 x 10(-4) cm(-1) and |E| approximately 50 x 10(-4) cm(-1). The increased hyperfine coupling with (31)P in the presence of TF1 reflects the specific interaction between the central Mn(2+) and the ADP beta-phosphate, illustrating the role of the enzyme active site in positioning the phosphate chain of the substrate for efficient catalysis. Results with the ternary Mn.TF1.ATP and Mn.TF1.AMP-PNP complexes are interpreted in a similar way with two hyperfine couplings being resolved for each complex (|A((31)P(beta))| approximately 4.60 MHz and |A((31)P(gamma))| approximately 5.90 MHz with ATP, and |A((31)P(beta))| approximately 4.20 MHz and |A((31)P(gamma))| approximately 5.40 MHz with AMP-PNP). In these complexes, the increased hyperfine coupling with (31)P(gamma) compared with (31)P(beta) reflects the smaller Mn.P distance with the gamma-phosphate compared with the beta-phosphate as found in the crystal structure of the analogous enzyme from mitochondria [3.53 vs 3.70 A (Abrahams, J. P., Leslie, A. G. W., Lutter, R., and Walker, J. E. (1994) Nature 370, 621-628)] and the different binding modes of the two phosphate groups. The ESEEM and HYSCORE data of a complex formed with Mn(2+), ATP, and the isolated beta subunit show that the (31)P hyperfine coupling is close to that measured in the absence of the protein, indicating a poorly structured nucleotide site in the isolated beta subunit in the presence of ATP. The inhibition data obtained for TF1 incubated in the presence of Mg(2+), ADP, Al(NO(3))(3), and NaF indicate the formation of the inhibited complex with the transition state analogue namely Mg.TF1.ADP.AlF(x) with the equilibrium dissociation constant K(D) = 350 microM and rate constant k = 0.02 min(-1). The ESEEM and HYSCORE data obtained for an inhibited TF1 sample, Mn.TF1.ADP.AlF(x), confirm the formation of the transition state analogue with distinct spectroscopic footprints that can be assigned to Mn.(19)F and Mn.(27)Al hyperfine interactions. The (31)P(beta) hyperfine coupling that is measured in the inhibited complex with the transition state analogue (|A((31)P(beta))| approximately 5.10 MHz) is intermediate between those measured in the presence of ADP and ATP and suggests an increase in the bond between Mn and the P(beta) from ADP upon formation of the transition state.

The hyperfine excitation of OH radicals by He

NASA Astrophysics Data System (ADS)

Marinakis, Sarantos; Kalugina, Yulia; Lique, François

2016-04-01

Hyperfine-resolved collisions between OH radicals and He atoms are investigated using quantum scattering calculations and the most recent ab initio potential energy surface, which explicitly takes into account the OH vibrational motion. Such collisions play an important role in astrophysics, in particular in the modelling of OH masers. The hyperfine-resolved collision cross sections are calculated for collision energies up to 2500 cm-1 from the nuclear spin free scattering S-matrices using a recoupling technique. The collisional hyperfine propensities observed are discussed. As expected, the results from our work suggest that there is a propensity for collisions with ΔF = Δj. The new OH-He hyperfine cross sections are expected to significantly help in the modelling of OH masers from current and future astronomical observations. Contribution to the Topical Issue "Atomic Cluster Collisions (7th International Symposium)", edited by Gerardo Delgado Barrio, Andrey Solov'Yov, Pablo Villarreal, Rita Prosmiti.

Multiple stable states of a periodically driven electron spin in a quantum dot using circularly polarized light

NASA Astrophysics Data System (ADS)

Korenev, V. L.

2011-06-01

The periodical modulation of circularly polarized light with a frequency close to the electron spin resonance frequency induces a sharp change of the single electron spin orientation. Hyperfine interaction provides a feedback, thus fixing the precession frequency of the electron spin in the external and the Overhauser field near the modulation frequency. The nuclear polarization is bidirectional and the electron-nuclear spin system (ENSS) possesses a few stable states. The same physics underlie the frequency-locking effect for two-color and mode-locked excitations. However, the pulsed excitation with mode-locked laser brings about the multitudes of stable states in ENSS in a quantum dot. The resulting precession frequencies of the electron spin differ in these states by the multiple of the modulation frequency. Under such conditions ENSS represents a digital frequency converter with more than 100 stable channels.

Intracavity Laser Absorption Spectroscopy of Platinum Nitride in the Near Infrared

NASA Astrophysics Data System (ADS)

O'Brien, Leah C.; Womack, Kaitlin A.; O'Brien, James J.; Whittemore, Sean

2013-06-01

The (2,0) band of the A^{2}Σ^{-} - X^{2}Π_{1/2} electronic transition of PtN has been recorded using intracavity laser absorption spectroscopy. Transitions from ^{194}PtN, ^{195}PtN, and ^{196}PtN isotopologues are observed, as well as the nuclear hyperfine splitting due to ^{195}Pt with I=1/2. The results of the analysis will be presented and compared with ab initio calculations.

Stochastic hyperfine interactions modeling library-Version 2

NASA Astrophysics Data System (ADS)

Zacate, Matthew O.; Evenson, William E.

2016-02-01

The stochastic hyperfine interactions modeling library (SHIML) provides a set of routines to assist in the development and application of stochastic models of hyperfine interactions. The library provides routines written in the C programming language that (1) read a text description of a model for fluctuating hyperfine fields, (2) set up the Blume matrix, upon which the evolution operator of the system depends, and (3) find the eigenvalues and eigenvectors of the Blume matrix so that theoretical spectra of experimental techniques that measure hyperfine interactions can be calculated. The optimized vector and matrix operations of the BLAS and LAPACK libraries are utilized. The original version of SHIML constructed and solved Blume matrices for methods that measure hyperfine interactions of nuclear probes in a single spin state. Version 2 provides additional support for methods that measure interactions on two different spin states such as Mössbauer spectroscopy and nuclear resonant scattering of synchrotron radiation. Example codes are provided to illustrate the use of SHIML to (1) generate perturbed angular correlation spectra for the special case of polycrystalline samples when anisotropy terms of higher order than A22 can be neglected and (2) generate Mössbauer spectra for polycrystalline samples for pure dipole or pure quadrupole transitions.

Mossbauer effect in dilute iron alloys

NASA Technical Reports Server (NTRS)

Singh, J. J.

1975-01-01

The effects of variable concentration, x, of Aluminum, Germanium, and Lanthanum atoms in Iron lattice on various Mossbauer parameters was studied. Dilute binary alloys of (Fe-Al), (Fe-Ge), (Fe-Al) containing up to x = 2 a/o of the dilute constituent were prepared in the form of ingots and rolled to a thickness of 0.001 in. Mossbauer spectra of these targets were then studied in transmission geometry to measure changes in the hyperfine field, peak widths isomer shifts as well as the ratio of the intensities of peaks (1,6) to the intensities of peaks (2,5). It was shown that the concept of effective hyperfine structure field in very dilute alloys provides a useful means of studying the effects of progressively increasing the solute concentration on host lattice properties.

Internal state control of a dense sample of ultracold 23Na87Rb molecules

NASA Astrophysics Data System (ADS)

Ye, Xin; Guo, Mingyang; He, Junyu; Wang, Dajun; Quemener, Goulven; Gonzalez-Martinez, Maykel; Dulieu, Oliver

2017-04-01

We report the optimized production of ultracold 23Na87Rb molecules with completely controlled population distribution among internal states. Starting from a sample of 104 weakly bound Feshbach molecules, we achieved a hyperfine-structure-resolved STIRAP transfer to the ground state with an efficiency up to 95%. By tuning the frequency difference between the Raman lasers and applying an additional microwave signal, we realized the preparation of NaRb samples in different vibrational, rotational, and hyperfine levels. Based on this achievement, some results on molecular collisions with a range of possible loss channels will also be reported. This work was supported by the French ANR/Hong Kong RGC COPOMOL project (Grant No. A-CUHK403/13), the RGC General Research Fund (Grant No. CUHK14301815).

Studies of Landé gJ-factors of singly ionized lanthanum by laser-induced fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Werbowy, S.; Güney, C.; Windholz, L.

2016-08-01

Laser-induced fluorescence spectroscopy, using a cooled hollow cathode discharge lamp as source of ions, was used to observe the Zeeman splitting of 18 lines of La II in the wavelength range 629.6-680.9 nm, in external intermediate magnetic fields up to 800 G. The recorded hyperfine-Zeeman patterns were analyzed in detail using already known accurate hyperfine structure A- and B-constants. From the recordings the Landé gJ-factors for some levels belonging to the 5d2, 5d6s, 5d6p, 4f5d, 4f6s and 4f6p configurations of La II were determined. The obtained experimental gJ-factors are compared with earlier measurements and theoretical calculations.

Quantum Chemical Calculations of Torsionally Mediated Hyperfine Splittings in States of E Symmetry of Acetaldehyde (CH_{3}CHO)

NASA Astrophysics Data System (ADS)

Xu, Li-Hong; Reid, Elias M.; Guislain, Bradley; Hougen, Jon T.; Alekseev, E. A.; Krapivin, Igor

2017-06-01

Hyperfine splittings in methanol have been revisited in three recent publications. (i) Coudert et al. [JCP 143 (2015) 044304] published an analysis of splittings observed in the low-J range. They calculated 32 spin-rotation, 32 spin-spin, and 16 spin-torsion hyperfine constants using the ACES2 package. Three of these constants were adjusted to fit hyperfine patterns for 12 transitions. (ii) Three present authors and collaborators [JCP 145 (2016) 024307] analyzed medium to high-J experimental Lamb-dip measurements in methanol and presented a theoretical spin-rotation explanation that was based on torsionally mediated spin-rotation hyperfine operators. These contain, in addition to the usual nuclear spin and overall rotational operators, factors in the torsional angle α of the form {e^{plusmn;{inα}}}. Such operators have non-zero matrix elements between the two components of a torsion-rotation ^{tr}E state, but have zero matrix elements within a ^{tr}A state. More than 55 hyperfine splittings were successfully fitted using three parameters and the fitted values agree well with ab initio values obtained in (i). (iii) Lankhaar et al. [JCP 145 (2016) 244301] published a reanalysis of the data set from (i), using CFOUR recalculated hyperfine constants based on their rederivation of the relevant expressions. They explain why their choice of fixed and floated parameters leads to numerical values for all parameters that seem to be more physical than those in (i). The results in (ii) raise the question of whether large torsionally-mediated spin-rotation splittings will occur in other methyl-rotor-containing molecules. This abstract presents ab initio calculations of torsionally mediated hyperfine splittings in the E states of acetaldehyde using the same three operators as in (ii) and spin-rotation constants computed by Gaussian09. We explored the first 13 K states for J from 10 to 40 and ν_{t} = 0, 1, and 2. Our calculations indicate that hyperfine splittings in CH_{3}CHO are just below current measurement capability. This conclusion is confirmed by available experimental measurements.

Effects of annealing temperature on structure and magnetic properties of CoAl0.2Fe1.8O4/SiO2 nanocomposites

NASA Astrophysics Data System (ADS)

Wang, L.; Li, J.; Liu, M.; Zhang, Y. M.; Lu, J. B.; Li, H. B.

2012-12-01

CoAl0.2Fe1.8O4/SiO2 nanocomposites were prepared by sol-gel method. The effects of annealing temperature on the structure and magnetic properties of the samples were studied by X-ray diffraction, transmission electron microscopy, vibrating sample magnetometer and Mössbauer spectroscopy. The results show that the CoAl0.2Fe1.8O4 in the samples exhibits a spinel structure after being annealed. As annealing temperature increases from 800 to 1200 °C, the average grain size of CoAl0.2Fe1.8O4 in the nanocomposites increases from 5 to 41 nm while the lattice constant decreases from 0.8397 to 0.8391 nm, the saturation magnetization increases from 21.96 to 41.53 emu/g. Coercivity reaches a maximum of 1082 Oe for the sample annealed at 1100 °C, and thereafter decreases with further increasing annealing temperature. Mössbauer spectra show that the isomer shift decreases, hyperfine field increases and the samples transfer from mixed state of superparamagnetic and magnetic order to the completely magnetic order with annealing temperature increasing from 800 to 1200 °C.

Structural, magnetic and hyperfine characterization of ZnxFe3-xO4 nanoparticles prepared by sol-gel approach via inorganic precursors

NASA Astrophysics Data System (ADS)

Kotsikau, Dzmitry; Pankov, Vladimir; Petrova, Elena; Natarov, Valentin; Filimonov, Dmitry; Pokholok, Konstantin

2018-03-01

Structural characteristics and magnetic properties of ZnxFe3-xO4 (where x = 0; 0.09; 0.18; 0.45; 1) nanoparticles were studied with X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared spectroscopy (IR) and vibrating sample magnetometry (VSM). Oxidation of Fe2+ ions, redistribution of Zn2+ and Fe3+ ions between octahedral and tetrahedral sites, and the formation of cation vacancies in spinel-type cubic structure of the obtained ZnxFe3-x-y□yO4 substitutional solid solutions were revealed by 57Fe Mössbauer spectroscopy. The nanoparticles synthesized via a modified sol-gel method using inorganic precursors have a size of 4-10 nm, single-phase composition, superparamagnetic behavior at room temperature (300 K) and a relatively hydrophilic surface to form stable aqueous suspensions. The maximum magnetization of 59 emu/g at 300 K corresponds to Zn0.18Fe2.82O4 composition. The listed features make the materials promising candidates for various biological and medical applications such as contrast-enhanced magnetic resonance imaging, hyperthermia of pathological tissues, controlled drug release, and separation of nucleic acids.

Electric dipole hyperfine structure of TIF

NASA Astrophysics Data System (ADS)

Hinds, Edward A.; Sandars, P. G. H.

1980-02-01

The authors have calculated the electric dipole interaction energy of the 205TI nucleus in TIF assuming a nonzero electric dipole moment dp on the proton. The result is used in the accompanying experimental paper to obtain a new value of (-1.4+/-6)×10-21 e cm for dp.

Beam maser measurements of CH3OH rotational transitions

NASA Technical Reports Server (NTRS)

Gaines, L.; Casleton, K. H.; Kukolich, S. G.

1974-01-01

Precise measurements of rotational transitions in methanol are reported that were made by means of beam maser spectrometers. No hyperfine structure was resolved at a resonance line width of 8 kHz. Accurate center frequencies for the transitions measured are useful for determining Doppler shifts for observed interstellar lines.

Moessbauer Study of Reduced Putidaredoxin in Zero and Intermediate Applied Fields.

NASA Astrophysics Data System (ADS)

Valentine, Mark

An ('57)Fe Mossbauer investigation of the reduced (S = 1/2) active center of the redox and effector protein, putidaredoxin, is reported. Putidaredoxin is a prototype of a 2Fe-2S protein; it functions as an electron shuttle in a bacterial enzyme system. Several 2Fe-2S proteins, including putidaredoxin, have already been subjected to numerous Mossbauer and magnetic resonance studies, but current understanding of the active center is still very incomplete, and the mechanism of electron transfer is not known. Previous Mossbauer experiments on reduced putidaredoxin, as on most Kramers systems, were restricted to the applied field range .01 - 4T. The intermediate field region 0 - .01T is included here, and a primary goal of this work is to demonstrate the feasibility of those experiments. The analysis of zero field spectra differs from that in applied fields in the following respects: (i) The spectra consist of 64 discrete lines. (ii) The average over all molecular orientations is done explicitly, not numerically. (iii) No generality is lost by taking the magnetic hyperfine terms for both sites to be symmetric and in their principal axis systems. (iv) The spectra are sensitive to weak coupling of S with nearby nuclear moments that become negligible as the applied field is increased. Skew-symmetric contributions to the magnetic hyperfine and electronic Zeeman interactions are often ignored in the literature without justification. Either g or A can be symmetrized by an S transformation, but both g and A can be simultaneously symmetrized if and only if the invariants. (DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI). are equal.

High-precision optical measurement of the 2S hyperfine interval in atomic hydrogen.

PubMed

Kolachevsky, N; Fischer, M; Karshenboim, S G; Hänsch, T W

2004-01-23

We have applied an optical method to the measurement of the 2S hyperfine interval in atomic hydrogen. The interval has been measured by means of two-photon spectroscopy of the 1S-2S transition on a hydrogen atomic beam shielded from external magnetic fields. The measured value of the 2S hyperfine interval is equal to 177 556 860(16) Hz and represents the most precise measurement of this interval to date. The theoretical evaluation of the specific combination of 1S and 2S hyperfine intervals D21 is in fair agreement (within 1.4 sigma) with the value for D21 deduced from our measurement.

Electron Tunneling in Lithium Ammonia Solutions Probed by Frequency-Dependent Electron-Spin Relaxation Studies

PubMed Central

Maeda, Kiminori; Lodge, Matthew T.J.; Harmer, Jeffrey; Freed, Jack H.; Edwards, Peter P.

2012-01-01

Electron transfer or quantum tunneling dynamics for excess or solvated electrons in dilute lithium-ammonia solutions have been studied by pulse electron paramagnetic resonance (EPR) spectroscopy at both X- (9.7 GHz) and W-band (94 GHz) frequencies. The electron spin-lattice (T1) and spin-spin (T2) relaxation data indicate an extremely fast transfer or quantum tunneling rate of the solvated electron in these solutions which serves to modulate the hyperfine (Fermi-contact) interaction with nitrogen nuclei in the solvation shells of ammonia molecules surrounding the localized, solvated electron. The donor and acceptor states of the solvated electron in these solutions are the initial and final electron solvation sites found before, and after, the transfer or tunneling process. To interpret and model our electron spin relaxation data from the two observation EPR frequencies requires a consideration of a multi-exponential correlation function. The electron transfer or tunneling process that we monitor through the correlation time of the nitrogen Fermi-contact interaction has a time scale of (1–10)×10−12 s over a temperature range 230–290K in our most dilute solution of lithium in ammonia. Two types of electron-solvent interaction mechanisms are proposed to account for our experimental findings. The dominant electron spin relaxation mechanism results from an electron tunneling process characterized by a variable donor-acceptor distance or range (consistent with such a rapidly fluctuating liquid structure) in which the solvent shell that ultimately accepts the transferring electron is formed from random, thermal fluctuations of the liquid structure in, and around, a natural hole or Bjerrum-like defect vacancy in the liquid. Following transfer and capture of the tunneling electron, further solvent-cage relaxation with a timescale of ca. 10−13 s results in a minor contribution to the electron spin relaxation times. This investigation illustrates the great potential of multi-frequency EPR measurements to interrogate the microscopic nature and dynamics of ultra fast electron transfer or quantum-tunneling processes in liquids. Our results also impact on the universal issue of the role of a host solvent (or host matrix, e.g. a semiconductor) in mediating long-range electron transfer processes and we discuss the implications of our results with a range of other materials and systems exhibiting the phenomenon of electron transfer. PMID:22568866

Fluctuating hyperfine interactions: an updated computational implementation

NASA Astrophysics Data System (ADS)

Zacate, M. O.; Evenson, W. E.

2015-04-01

The stochastic hyperfine interactions modeling library (SHIML) is a set of routines written in the C programming language designed to assist in the analysis of stochastic models of hyperfine interactions. The routines read a text-file description of the model, set up the Blume matrix, upon which the evolution operator of the quantum mechanical system depends, and calculate the eigenvalues and eigenvectors of the Blume matrix, from which theoretical spectra of experimental techniques can be calculated. The original version of SHIML constructs Blume matrices applicable for methods that measure hyperfine interactions with only a single nuclear spin state. In this paper, we report an extension of the library to provide support for methods such as Mössbauer spectroscopy and nuclear resonant scattering of synchrotron radiation, which are sensitive to interactions with two nuclear spin states. Examples will be presented that illustrate the use of this extension of SHIML to generate Mössbauer spectra for polycrystalline samples under a number of fluctuating hyperfine field models.

Theoretical studies of alkyl radicals in the NaY and HY zeolites.

PubMed

Ghandi, Khashayar; Zahariev, Federico E; Wang, Yan Alexander

2005-08-18

Interplay of quantum mechanical calculations and experimental data on hyperfine coupling constants of ethyl radical in zeolites at several temperatures was engaged to study the geometries and binding energies and to predict the temperature dependence of hyperfine splitting of a series of alkyl radicals in zeolites for the first time. The main focus is on the hyperfine interaction of alkyl radicals in the NaY and HY zeolites. The hyperfine splitting for neutral free radicals and free radical cations is predicted for different zeolite environments. This information can be used to establish the nature of the muoniated alkyl radicals in the NaY and HY zeolites via muSR experiments. The muon hyperfine coupling constants of the ethane radical cation in these zeolites are very large with relatively little dependence on temperature. It was found that the intramolecular dynamics of alkyl free radicals are only weakly affected by their strong binding to zeolites. In contrast, the substrate binding has a significant effect on their intermolecular dynamics.

The DFT Calculations of Structures and EPR Parameters for the Dinuclear Paddle-Wheel Copper(II) Complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) as Powder or Single Crystal

NASA Astrophysics Data System (ADS)

Ding, Chang-Chun; Wu, Shao-Yi; Xu, Yong-Qiang; Zhang, Li-Juan; Zhang, Zhi-Hong; Zhu, Qin-Sheng; Wu, Ming-He; Teng, Bao-Hua

2017-10-01

Density functional theory (DFT) calculations of the structures and the Cu2+ g factors (gx, gy and gz ) and hyperfine coupling tensor A (Ax , Ay and Az ) were performed for the paddle-wheel (PW)-type binuclear copper(II) complex {Cu2(μ2-O2CCH3)4}(OCNH2CH3) powder and single crystal. Calculations were carried out with the ORCA software using the functionals BHandHlyp, B3P86 and B3LYP with five different basis sets: 6-311g, 6-311g(d,p), VTZ, def-2 and def2-TZVP. Results were tested by the MPAD analysis to find the most suitable functional and basis sets. The electronic structure and covalency between copper and oxygen were investigated by the electron localisation function and the localised orbital locator as well as the Mayer bond order for the [CuO5] group. The optical spectra were theoretically calculated by the time-dependent DFT module and plotted by the Multiwfn program for the [CuO5] group and reasonably associated with the local structure in the vicinity of the central ion copper. In addition, the interactions between the OCNH2CH3, NH3 and H2O molecules and the uncoordinated PW copper(II) complex were studied, and the corresponding adsorption energies, the frequency shifts with respect to the free molecules and the changes of the Cu-Cu distances were calculated and compared with the relevant systems.

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

Harvey-Collard, Patrick; Jacobson, N. Tobias; Rudolph, Martin

Individual donors in silicon chips are used as quantum bits with extremely low error rates. However, physical realizations have been limited to one donor because their atomic size causes fabrication challenges. Quantum dot qubits, in contrast, are highly adjustable using electrical gate voltages. This adjustability could be leveraged to deterministically couple donors to quantum dots in arrays of qubits. In this work, we demonstrate the coherent interaction of a 31P donor electron with the electron of a metal-oxide-semiconductor quantum dot. We form a logical qubit encoded in the spin singlet and triplet states of the two-electron system. We show thatmore » the donor nuclear spin drives coherent rotations between the electronic qubit states through the contact hyperfine interaction. This provides every key element for compact two-electron spin qubits requiring only a single dot and no additional magnetic field gradients, as well as a means to interact with the nuclear spin qubit.« less

Innovation and reliability of atomic standards for PTTI applications

NASA Technical Reports Server (NTRS)

Kern, R.

1981-01-01

Innovation and reliability in hyperfine frequency standards and clock systems are discussed. Hyperfine standards are defined as those precision frequency sources and clocks which use a hyperfine atomic transition for frequency control and which have realized significant commercial production and acceptance (cesium, hydrogen, and rubidium atoms). References to other systems such as thallium and ammonia are excluded since these atomic standards have not been commercially exploited in this country.

Material science and solid state physics studies with positive muon spin precession. [fe(a1) alloys

NASA Technical Reports Server (NTRS)

Stronach, C. E.

1979-01-01

The hyperfine field on the muon, B sub hf, at interstitial sites in dilute Fe(Al) alloys was measured for four different concentrations of Al and as a function of temperature by the muon spin rotation method. The magnitude of B sub hf, which is negative, decreases at rates ranging from 0.09 + or - 0.03% per at.% Al at 200 K to an asymptotic limit of 0.35 + or - far above 440 K. This behavior shows that sites near the Al impurity are weakly repulsive to the muon, with an interaction potential of 13 + or - 3 meV. In order to fit the temperature dependence of the hyperfine field, it is necessary to hypothesize the existence of a small concentration of unidentified defects, possibly dislocations, which are attractive to the muon. Although the Al impurity acts as a non-magnetic hole in the Fe lattice, the observed decrease in B sub hf is only 35% of the decrease in the bulk magnetization. It is concluded that B sub hf is determined mainly by the enhanced screening of conduction electrons in Fe and Fe(Al). Since the influence of the Al impurity on the neighboring Fe monents is very small, most of the change in B sub hf is therefore attributed to the increase in conduction electron polarization of the Al impurity.

Hyperfine fields and anisotropy of the orbital moment in epitaxial Mn5Ge3 films studied by 55Mn NMR

NASA Astrophysics Data System (ADS)

Kalvig, R.; Jedryka, E.; Wojcik, M.; Allodi, G.; De Renzi, R.; Petit, M.; Michez, L.

2018-05-01

55Mn NMR was used to perform the atomic-scale study of the anisotropic properties of Mn5Ge3 /Ge(111) epitaxial films with thicknesses between 9 and 300 nm. The NMR spectra have been recorded as a function of strong external magnetic field applied in the film plane and perpendicular to it. Two 55Mn NMR resonances have been observed, corresponding to the two manganese sites 4 d and 6 g , in the hexagonal D 88 structure; in zero field their frequency is centered around 207.5 and 428 MHz, respectively. The anisotropy of 55Mn hyperfine fields between the hexagonal c direction and the c plane at both Mn sites was evidenced and attributed to the anisotropic term due to the unquenched Mn orbital momentum. The anisotropy of the orbital contribution to hyperfine fields was determined as 1.52 T in the 4 d site and up to 2.77 T in the 6 g site. The 4 d site reveals a quadrupolar interaction due to the strong electric field gradient: Vz z=5.3 ×1019V/m2 in this site, which is shown to be oriented along the hexagonal c axis.

Mineralogical characterization of Greda clays and monitoring of their phase transformations on thermal treatment

NASA Astrophysics Data System (ADS)

Panduro, E. Chavez; Cabrejos, J. Bravo

2010-01-01

The mineralogical characterization of two clay samples from the Central Andean Region of Peru, denominated White Greda and Red Greda, is reported. These clays contain the clay minerals mica and illite respectively. Both clays were treated thermally in an oxidising atmosphere under controlled conditions up to 1,100°C with the purpose of obtaining information about structural changes that may be useful for pottery manufacture. X-ray fluorescence was used for the elemental characterization of the samples and X-ray diffractometry was used to determine the collapse and formation of the mineral phases present in the samples caused by thermal treatment. At temperatures above 1,000°C it is observed the formation of spinel in the case of White Greda and of hematite, corundum and cristobalite in the case of Red Greda. Room temperature transmission Mössbauer spectroscopy allowed the monitoring of the variation of the hyperfine parameters with the thermal treatment temperature; In the case of the evolution of the quadruple splitting of the paramagnetic Fe3 + sites with temperature, in both clays, the analyses reproduced results such as the “camel back” curve shape, found by other workers (Wagner and Wagner, Hyperfine Interact 154:35-82, 2004; Wagner and Kyek, Hyperfine Interact 154:5-33, 2004).

Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses.

PubMed

Miglierini, Marcel B; Procházka, Vít; Vrba, Vlastimil; Švec, Peter; Janičkovič, Dušan; Matúš, Peter

2018-06-07

We demonstrate the use of two nuclear-based analytical methods that can follow the modifications of microstructural arrangement of iron-based metallic glasses (MGs). Despite their amorphous nature, the identification of hyperfine interactions unveils faint structural modifications. For this purpose, we have employed two techniques that utilize nuclear resonance among nuclear levels of a stable 57 Fe isotope, namely Mössbauer spectrometry and nuclear forward scattering (NFS) of synchrotron radiation. The effects of heat treatment upon (Fe2.85Co1)77Mo8Cu1B14 MG are discussed using the results of ex situ and in situ experiments, respectively. As both methods are sensitive to hyperfine interactions, information on structural arrangement as well as on magnetic microstructure is readily available. Mössbauer spectrometry performed ex situ describes how the structural arrangement and magnetic microstructure appears at room temperature after the annealing under certain conditions (temperature, time), and thus this technique inspects steady states. On the other hand, NFS data are recorded in situ during dynamically changing temperature and NFS examines transient states. The use of both techniques provides complementary information. In general, they can be applied to any suitable system in which it is important to know its steady state but also transient states.

The millimeter-wave spectrum of the MgH and MgD radicals

NASA Technical Reports Server (NTRS)

Ziurys, L. M.; Barclay, W. L., Jr.; Anderson, M. A.

1993-01-01

The pure rotational spectrum of MgH radical (X 2 Sigma (+)) in its ground state v = 0 and v = 1 vibrational modes has been observed in the laboratory using millimeter/submillimeter direct absorption spectroscopy. The rotational spectra of two isotopically substituted species, MgD and (Mg-26)H, have been detected as well. All six hyperfine components of the N = 0 -1 transition of MgH in its v = 0 and v = 1 states have been directly measured to an accuracy of +/-50 kHz, and the five components have been observed for (Mg-26)H. The N = 0 +/-1 and N = 1 -2 transitions of MgD have also been detected. Rotational, fine structure, and hyperfine constants were determined for all species from a nonlinear least-squared fit to the data using a 2 Sigma Hamiltonian.

Manipulation of individual hyperfine states in cold trapped molecular ions and application to HD+ frequency metrology.

PubMed

Bressel, U; Borodin, A; Shen, J; Hansen, M; Ernsting, I; Schiller, S

2012-05-04

Advanced techniques for manipulation of internal states, standard in atomic physics, are demonstrated for a charged molecular species for the first time. We address individual hyperfine states of rovibrational levels of a diatomic ion by optical excitation of individual hyperfine transitions, and achieve controlled transfer of population into a selected hyperfine state. We use molecular hydrogen ions (HD+) as a model system and employ a novel frequency-comb-based, continuous-wave 5  μm laser spectrometer. The achieved spectral resolution is the highest obtained so far in the optical domain on a molecular ion species. As a consequence, we are also able to perform the most precise test yet of the ab initio theory of a molecule.

Characterization of the hyperfine interaction of the excited D50 state of Eu3 +:Y2SiO5

NASA Astrophysics Data System (ADS)

Cruzeiro, Emmanuel Zambrini; Etesse, Jean; Tiranov, Alexey; Bourdel, Pierre-Antoine; Fröwis, Florian; Goldner, Philippe; Gisin, Nicolas; Afzelius, Mikael

2018-03-01

We characterize the europium (Eu3 +) hyperfine interaction of the excited state (D50) and determine its effective spin Hamiltonian parameters for the Zeeman and quadrupole tensors. An optical free induction decay method is used to measure all hyperfine splittings under a weak external magnetic field (up to 10 mT) for various field orientations. On the basis of the determined Hamiltonian, we discuss the possibility to predict optical transition probabilities between hyperfine levels for the F70⟷D50 transition. The obtained results provide necessary information to realize an optical quantum memory scheme which utilizes long spin coherence properties of 3 + 151Eu :Y2SiO5 material under external magnetic fields.

Oxygen-related 1-platinum defects in silicon: An electron paramagnetic resonance study

NASA Astrophysics Data System (ADS)

Juda, U.; Scheerer, O.; Höhne, M.; Riemann, H.; Schilling, H.-J.; Donecker, J.; Gerhardt, A.

1996-09-01

A monoclinic 1-platinum defect recently detected was investigated more thoroughly by electron paramagnetic resonance (EPR). The defect is one of the dominating defects in platinum doped silicon. With a perfect reproducibility it is observed in samples prepared from n-type silicon as well as from p-type silicon, in float zone (FZ) silicon as well as in Czochralski (Cz) silicon. Its concentration varies with the conditions of preparation and nearly reaches that of isolated substitutional platinum in Cz silicon annealed for 2 h at 540 °C after quenching from the temperature of platinum diffusion. Because of its concentration which in Cz-Si exceeds that in FZ-Si the defect is assumed to be oxygen-related though a hyperfine structure with 17O could not be resolved. The defect causes a level close to the valence band. This is concluded from variations of the Fermi level and from a discussion of the spin Hamiltonian parameters. In photo-EPR experiments the defect is coupled to recently detected acceptorlike self-interstitial related defects (SIRDs); their level position turns out to be near-midgap. These defects belong to the lifetime limiting defects in Pt-doped Si.

Free radicals generated during oxidation of green tea polyphenols: electron paramagnetic resonance spectroscopy combined with density functional theory calculations.

PubMed

Severino, Joyce Ferreira; Goodman, Bernard A; Kay, Christopher W M; Stolze, Klaus; Tunega, Daniel; Reichenauer, Thomas G; Pirker, Katharina F

2009-04-15

Electron paramagnetic resonance spectroscopy and density functional theory calculations have been used to investigate the redox properties of the green tea polyphenols (GTPs) (-)-epigallocatechin gallate (EGCG), (-)-epigallocatechin (EGC), and (-)-epicatechin gallate (ECG). Aqueous extracts of green tea and these individual phenols were autoxidized at alkaline pH and oxidized by superoxide anion (O(2)(-)) radicals in dimethyl sulfoxide. Several new aspects of the free radical chemistry of GTPs were revealed. EGCG can be oxidized on both the B and the D ring. The B ring was the main oxidation site during autoxidation, but the D ring was the preferred site for O(2)(-) oxidation. Oxidation of the D ring was followed by structural degradation, leading to generation of a radical identical to that of oxidized gallic acid. Alkaline autoxidation of green tea extracts produced four radicals that were related to products of the oxidation of EGCG, EGC, ECG, and gallic acid, whereas the spectra from O(2)(-) oxidation could be explained solely by radicals generated from EGCG. Assignments of hyperfine coupling constants were made by DFT calculations, allowing the identities of the radicals observed to be confirmed.

Proposal for Laser Cooling of Alkaline Earth Monoalkoxide Free Radicals

NASA Astrophysics Data System (ADS)

Baum, Louis; Kozyryev, Ivan; Matsuda, Kyle; Doyle, John M.

2016-05-01

Cold samples of polyatomic molecules will open new avenues in physics, chemistry, and quantum science. Non-diagonal Franck-Condon factors, technically challenging wavelengths, and the lack of strong electronic transitions inhibit direct laser cooling of nonlinear molecules. We identify a scheme for optical cycling in certain molecules with six or more atoms. Replacing hydrogen in alcohols with an alkaline earth metal (M) leads to alkaline earth monoalkoxide free radicals (MOR), which have favorable properties for laser cooling. M-O bond is very ionic, so the metal orbitals are slightly affected by the nature of R on the ligand. Diagonal Franck-Condon factors, laser accessible transitions, and a small hyperfine structure make MOR molecules suitable for laser cooling. We explore a scheme for optical cycling on the A - X transition of SrOCH3 . Molecules lost to dark vibrational states will be repumped on the B - X transition. Extension to larger species is possible through expansion of the R group since transitions involve the promotion of the metal-centered nonbonding valence electron. We will detail our estimations of the Franck-Condon factors, simulations of the cooling process and describe progress towards the Doppler cooling of MOR polyatomics.

Effect of Jahn-Teller ion in zinc sodium sulphate hexahydrate: a case of low hyperfine coupling constant for Cu(II) ion

NASA Astrophysics Data System (ADS)

Naidu, K. C.; Shiyamala, C.; Mithira, S.; Natarajan, B.; Venkatesan, R.; Rao, P. S.

2005-06-01

Single crystal electron paramagnetic resonance (EPR) studies of Cu(II) doped zinc sodium sulphate hexahydrate are carried out from room temperature (RT) to 123 K. The RT spectra show unresolved hyperfine lines and hence angular variation studies are also carried out at 123 K to obtain spin Hamiltonian parameters. The spin Hamiltonian parameters calculated from the 123 K spectra are: g(11)=2.039, g(22)=2.232, g(33)=2.394, A(11)=5.64 mT, A(22)=4.20 mT, and A(33)=7.94 mT. The g-matrix values at RT and 123 K have matched fairly well with each other. The low hyperfine value (A(33)), obtained at 123 K, has been explained by considering considerable admixture of d(x 2-y 2) ground state with d(z 2) excited state and the delocalization of the unpaired spin density onto the ligands. The admixture coefficients of ground state wave function are: a=0.346, b=0.935, c=0.055, d=0.040, e=-0.040, where a and b correspond to admixture coefficients for d(z 2) and d(x 2-y 2), respectively. Angular variation of Cu(II) resonances in the three orthogonal axes shows that the impurity has entered a substitutional site in the host lattice in place of Zn(II). Bonding parameters, kappa=0.295, P=245.4x10(-4), alpha(2)=0.709, alpha=0.8421 and alpha'=0.6034, have also been calculated to fully characterize the EPR.

Extended calculations of energy levels, radiative properties, AJ, BJ hyperfine interaction constants, and Landé gJ-factors for nitrogen-like Ge XXVI

NASA Astrophysics Data System (ADS)

Wang, K.; Zhang, C. Y.; Jönsson, P.; Si, R.; Zhao, X. H.; Chen, Z. B.; Guo, X. L.; Chen, C. Y.; Yan, J.

2018-03-01

Employing two state-of-the-art methods, multiconfiguration Dirac-Hartree-Fock and second-order many-body perturbation theory, highly accurate calculations are performed for the lowest 272 fine-structure levels arising from the 2s22p3, 2s2p4, 2p5, 2s22p23l (l = s , p , d), 2s2p33l (l = s , p , d), and 2p43l (l = s , p , d) configurations in nitrogen-like Ge XXVI. Complete and consistent atomic data, including excitation energies, lifetimes, wavelengths, hyperfine structures, Landé gJ-factors, and E1, E2, M1, M2 line strengths, oscillator strengths, and transition rates among these 272 levels are provided. Comparisons are made between the present two data sets, as well as with other available experimental and theoretical values. The present data are accurate enough for identification and deblending of emission lines involving the n = 3 levels, and are also useful for modeling and diagnosing fusion plasmas.

Hyperfine structure measurements of neutral iodine atom (127I) using Fourier Transform Spectrometry

NASA Astrophysics Data System (ADS)

Ashok, Chilukoti; Vishwakarma, S. R.; Bhatt, Himal; Ankush, B. K.; Deo, M. N.

2018-01-01

We report the hyperfine Structure (hfs) splitting observations of neutral iodine atom (II) in the 6000 - 10,000 cm-1 near infrared spectral region. The measurements were carried out using a high-resolution Fourier Transform Spectrometer (FTS), where an electrodeless discharge lamp (EDL), excited using microwaves, was employed as the light source and InGaAs as the light detector. A specially designed setup was used to lower the plasma temperature of the medium so as to reduce the Doppler width and consequently to increase the spectral resolution of hfs components. A total of 183 lines with hfs splitting have been observed, out of which hfs in 53 spectral lines are reported for the first time. On the basis of hfs analysis, we derived the magnetic dipole and electric quadrupole coupling constants, A and B respectively for 30 even and 30 odd energy levels and are compared with the values available in the literature. New hfs values for 5 even and 4 odd levels are also reported here for the first time.

Theoretical research on the spin-Hamiltonian parameters of the rhombic W5+ centers in CaWO4:Y3+ crystal

NASA Astrophysics Data System (ADS)

Mei, Yang; Wei, Cheng-Fu; Zheng, Wen-Chen

2016-02-01

Detailed theoretical calculations for the spin-Hamiltonian parameters (g factors gi and hyperfine structure constants Ai, where i=x, y, z) of the rhombic W5+ center in CaWO4:Y3+ crystal are performed by using the high-order perturbation formulas for d1 ions in rhombic tetrahedral clusters with the ground state |dz2>. These formulas consist of the contributions from two mechanisms, the crystal-field (CF) mechanism connected with CF excited states in the vastly-used CF theory and the frequently-neglected charge-transfer (CT) mechanism related to CT excited states. The calculated results agree well with the experimental values. The calculations indicate that for W5+ ion (or other high valence state dn ions) in crystals, the model calculations of spin-Hamiltonian parameters should take both the CF and CT mechanisms into account. The signs of hyperfine structure constants Ai are suggested and the forming (or defect model) of rhombic W5+ center in CaWO4:Y3+ crystal is confirmed from the calculations.

Extending the electron spin coherence time of atomic hydrogen by dynamical decoupling.

PubMed

Mitrikas, George; Efthimiadou, Eleni K; Kordas, George

2014-02-14

We study the electron spin decoherence of encapsulated atomic hydrogen in octasilsesquioxane cages induced by the (1)H and (29)Si nuclear spin bath. By applying the Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence we significantly suppress the low-frequency noise due to nuclear spin flip-flops up to the point where a maximum T2 = 56 μs is observed. Moreover, dynamical decoupling with the CPMG sequence reveals the existence of two other sources of decoherence: first, a classical magnetic field noise imposed by the (1)H nuclear spins of the cage organic substituents, which can be described by a virtual fluctuating magnetic field with the proton Larmor frequency, and second, decoherence due to anisotropic hyperfine coupling between the electron and the inner (29)Si spins of the cage.

Gold atoms and clusters on MgO(100) films; an EPR and IRAS study

NASA Astrophysics Data System (ADS)

Yulikov, M.; Sterrer, M.; Risse, T.; Freund, H.-J.

2009-06-01

Single gold atoms deposited on single crystalline MgO(1 0 0) films grown on Mo(1 0 0) are characterized by electron paramagnetic resonance spectroscopy as well as IR spectroscopy using CO as probe molecules. In this article we describe the first angular dependent measurements to determine the principal hyperfine components of a secondary hyperfine interaction, namely, with 17O of the MgO. The values determined here are in perfect agreement with theoretical expectations and corroborate the previously reported binding mechanism of Au atoms on the oxygen anions of the MgO terrace. The temperature dependent EPR data reveal an onset of Au atom mobility at about 80 K while the formation of Au particles occurs only above 125 K. By an analysis of the EPR line width in combination with STM measurements it is possible to deduce an increase of the interatomic distance above 80 K. The Au/CO complexes show a somewhat smaller temperature stability as compared to the Au atoms. The observed thermal stability is in perfect agreement with theoretical predictions for CO desorption.

Search for variation of fundamental constants and violations of fundamental symmetries using isotope comparisons

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

Berengut, J. C.; Flambaum, V. V.; Kava, E. M.

2011-10-15

Atomic microwave clocks based on hyperfine transitions, such as the caesium standard, tick with a frequency that is proportional to the magnetic moment of the nucleus. This magnetic moment varies strongly between isotopes of the same atom, while all atomic electron parameters remain the same. Therefore the comparison of two microwave clocks based on different isotopes of the same atom can be used to constrain variation of fundamental constants. In this paper, we calculate the neutron and proton contributions to the nuclear magnetic moments, as well as their sensitivity to any potential quark-mass variation, in a number of isotopes ofmore » experimental interest including {sup 201,199}Hg and {sup 87,85}Rb, where experiments are underway. We also include a brief treatment of the dependence of the hyperfine transitions to variation in nuclear radius, which in turn is proportional to any change in quark mass. Our calculations of expectation values of proton and neutron spin in nuclei are also needed to interpret measurements of violations of fundamental symmetries.« less

ESR, electrochemical and cyclodextrin-inclusion studies of triazolopyridyl pyridyl ketones and dipyridyl ketones derivatives

NASA Astrophysics Data System (ADS)

Olea-Azar, C.; Abarca, B.; Norambuena, E.; Opazo, L.; Jullian, C.; Valencia, S.; Ballesteros, R.; Chadlaoui, M.

2008-11-01

The electron spin resonance (ESR) spectra of free radicals obtained by electrolytic reduction of triazolopyridyl pyridyl ketones and dipyridyl ketones derivatives were measured in dimethylsulfoxide (DMSO). The hyperfine patterns indicate that the spin density delocalization is dependent of the rings presented in the molecule. The electrochemistry of these compounds was characterized using cyclic voltammetry, in DMSO as solvent. When one carbonyl is present in the molecule one step in the reduction mechanism was observed while two carbonyl are present two steps were detected. The first wave was assigned to the generation of the correspondent free radical species, and the second wave was assigned to the dianion derivatives. The phase-solubility measurements indicated an interaction between molecules selected and cyclodextrins in water. These inclusion complexes are 1:1 with βCD, and HP-βCD. The values of Ks showed a different kind of complexes depending on which rings are included. AM1 and DFT calculations were performed to obtain the optimized geometries, theoretical hyperfine constants, and spin distributions, respectively. The theoretical results are in complete agreement with the experimental ones.

Linear Hyperfine Tuning of Donor Spins in Silicon Using Hydrostatic Strain

NASA Astrophysics Data System (ADS)

Mansir, J.; Conti, P.; Zeng, Z.; Pla, J. J.; Bertet, P.; Swift, M. W.; Van de Walle, C. G.; Thewalt, M. L. W.; Sklenard, B.; Niquet, Y. M.; Morton, J. J. L.

2018-04-01

We experimentally study the coupling of group V donor spins in silicon to mechanical strain, and measure strain-induced frequency shifts that are linear in strain, in contrast to the quadratic dependence predicted by the valley repopulation model (VRM), and therefore orders of magnitude greater than that predicted by the VRM for small strains |ɛ |<10-5. Through both tight-binding and first principles calculations we find that these shifts arise from a linear tuning of the donor hyperfine interaction term by the hydrostatic component of strain and achieve semiquantitative agreement with the experimental values. Our results provide a framework for making quantitative predictions of donor spins in silicon nanostructures, such as those being used to develop silicon-based quantum processors and memories. The strong spin-strain coupling we measure (up to 150 GHz per strain, for Bi donors in Si) offers a method for donor spin tuning—shifting Bi donor electron spins by over a linewidth with a hydrostatic strain of order 10-6—as well as opportunities for coupling to mechanical resonators.

Hyperfine Fields in Nanocrystalline Fe0.48Al0.52

NASA Astrophysics Data System (ADS)

Szymański, K.; Satuła, D.; Dobrzyński, L.; Voronina, E.; Yelsukov, E. P.

2004-12-01

Mössbauer measurements with circularly polarized radiation were performed on a nanocrystalline, disordered Fe48Al52 alloy. The analysis of the data for various polarization states resulted in the characterization of the hyperfine magnetic field distribution and the dependence of the average z-component of hyperfine field on the chemical environment. An increasing number of Al in the first coordination shell causes not only a decrease of magnetic moments but also introduces noncollinearity.

Carbonate Complexation of Mn2+ in Aqueous Phase

PubMed Central

Dasgupta, Jyotishman; Tyryshkin, Alexei M.; Kozlov, Yuri N.; Klimov, Vyacheslav V.; Dismukes, G. Charles

2008-01-01

The chemical speciation of Mn2+ within cells is critical for its transport, availability and redox properties. Herein we investigate the redox behavior and complexation equilibria of Mn2+ in aqueous solutions of bicarbonate by voltametry and electron paramagnetic resonance (EPR) spectroscopy, and discuss the implications for the uptake of Mn2+ by mangano-cluster enzymes like photosystem II (PSII). Both the electrochemical reduction of Mn2+ to Mn0 at an Hg electrode and EPR (in the absence of a polarizing electrode), revealed formation of 1:1 and 1:2 Mn-(bi)carbonate complexes as a function of Mn2+ and bicarbonate concentrations. Pulsed EPR spectroscopy, including ENDOR, ESEEM and 2D-HYSCORE, were used to probe the hyperfine couplings to 1H and 13C nuclei of the ligand(s) bound to Mn2+. For the 1:2 complex the complete 13C hyperfine tensor for one of the (bi)carbonate ligands was determined and it was established that this ligand coordinates to Mn2+ in bidentate mode with 13C-Mn distance of 2.85 ± 0.1 Å. The second (bi)carbonate ligand in the 1:2 complex coordinates possibly in monodentate mode, which is structurally less defined, and its 13C signal is broad and unobservable. 1H ENDOR reveals that 1-2 water ligands are lost upon binding of one bicarbonate ion in the 1:1 complex while 3-4 water ligands are lost upon forming the 1:2 complex. Thus, we deduce that the dominant species above 0.1 M bicarbonate concentration is the 1:2 complex, [Mn(CO3)(HCO3)(OH2)3]-. PMID:16526753

Power Scaling and Frequency Stabilization of an Injection-Locked Laser

DTIC Science & Technology

2000-05-01

In Chapter 4,1 alter the well -documented theory of locking a laser to a Fabry- Perot by performing the PDH error signal derivation in a new manner...the well -documented modulation transfer scheme to lock the frequency-doubled NPRO to a hyperfine component of an electronic transition in I2. 33 I...generally true at very low noise frequencies, well within the feedback loop bandwidth. However, when G0L(V„) « 1 and thus GCL(vn) « 1, Equation 3.9

Evidence for Nuclear Tensor Polarization of Deuterium Molecules in Storage Cells

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

van den Brand, J.; Bulten, H.; Zhou, Z.

1997-02-01

Deuterium molecules were obtained by recombination, on a copper surface, of deuterium atoms prepared in specific hyperfine states. The molecules were stored for about 5ms in an open-ended cylindrical cell, placed in a 23mT magnetic field, and their tensor polarization was measured by elastic scattering of 704MeV electrons. The results of the measurements are consistent with the deuterium molecules retaining the tensor polarization of the initial atoms. {copyright} {ital 1997} {ital The American Physical Society}

Activities report in nuclear physics and particle acceleration

NASA Astrophysics Data System (ADS)

Jansen, J. F. W.; Demeijer, R. J.

1984-04-01

Research on nuclear resonances; charge transfer; breakup of light and heavy ions; reaction mechanisms of heavy ion collisions; high-spin states; and fundamental symmetries in weak interactions are outlined. Group theoretical methods applied to supersymmetries; phenomenological description of rotation-vibration coupling; a microscopic theory of collective variables; the binding energy of hydrogen adsorbed on stepped platinium; and single electron capture are discussed. Isotopes for nuclear medicine, for off-line nuclear spectroscopy work, and for the study of hyperfine interactions were produced.

Combined 4-component and relativistic pseudopotential study of ThO for the electron electric dipole moment search.

PubMed

Skripnikov, L V

2016-12-07

A precise theoretical study of the electronic structure of heavy atom diatomic molecules is of key importance to interpret the experiments in the search for violation of time-reversal (T) and spatial-parity (P) symmetries of fundamental interactions in terms of the electron electric dipole moment, eEDM, and dimensionless constant, k T,P , characterizing the strength of the T,P-odd pseudoscalar-scalar electron-nucleus neutral current interaction. The ACME collaboration has recently improved limits on these quantities using a beam of ThO molecules in the electronic H 3 Δ 1 state [J. Baron et al., Science 343, 269 (2014)]. We apply the combined direct relativistic 4-component and two-step relativistic pseudopotential/restoration approaches to a benchmark calculation of the effective electric field, E eff , parameter of the T,P-odd pseudoscalar-scalar interaction, W T,P , and hyperfine structure constant in Δ13 state of the ThO molecule. The first two parameters are required to interpret the experimental data in terms of the eEDM and k T,P constant. We have investigated the electron correlation for all of the 98 electrons of ThO simultaneously up to the level of the coupled cluster with single, double, and noniterative triple amplitudes, CCSD(T), theory. Contributions from iterative triple and noniterative quadruple cluster amplitudes for the valence electrons have been also treated. The obtained values are E eff = 79.9 GV/cm, W T,P = 113.1 kHz. The theoretical uncertainty of these values is estimated to be about two times smaller than that of our previous study [L. V. Skripnikov and A. V. Titov, J. Chem. Phys., 142, 024301 (2015)]. It was found that the correlation of the inner- and outer-core electrons contributes 9% to the effective electric field. The values of the molecule frame dipole moment of the Δ13 state and the H 3 Δ 1 →X 1 Σ + transition energy of ThO calculated within the same methods are in a very good agreement with the experiment.

Characterization of Water Coordination to Ferrous Nitrosyl Complexes with fac-N2O, cis-N2O2, and N2O3 Donor Ligands.

PubMed

McCracken, John; Cappillino, Patrick J; McNally, Joshua S; Krzyaniak, Matthew D; Howart, Michael; Tarves, Paul C; Caradonna, John P

2015-07-06

Electron paramagnetic resonance (EPR) experiments were done on a series of S = (3)/2 ferrous nitrosyl model complexes prepared with chelating ligands that mimic the 2-His-1-carboxylate facial triad iron binding motif of the mononuclear nonheme iron oxidases. These complexes formed a comparative family, {FeNO}(7)(N2Ox)(H2O)3-x with x = 1-3, where the labile coordination sites for the binding of NO and solvent water were fac for x = 1 and cis for x = 2. The continuous-wave EPR spectra of these three complexes were typical of high-spin S = (3)/2 transition-metal ions with resonances near g = 4 and 2. Orientation-selective hyperfine sublevel correlation (HYSCORE) spectra revealed cross peaks arising from the protons of coordinated water in a clean spectral window from g = 3.0 to 2.3. These cross peaks were absent for the {FeNO}(7)(N2O3) complex. HYSCORE spectra were analyzed using a straightforward model for defining the spin Hamiltonian parameters of bound water and showed that, for the {FeNO}(7)(N2O2)(H2O) complex, a single water conformer with an isotropic hyperfine coupling, Aiso = 0.0 ± 0.3 MHz, and a dipolar coupling of T = 4.8 ± 0.2 MHz could account for the data. For the {FeNO}(7)(N2O)(H2O)2 complex, the HYSCORE cross peaks assigned to coordinated water showed more frequency dispersion and were analyzed with discrete orientations and hyperfine couplings for the two water molecules that accounted for the observed orientation-selective contour shapes. The use of three-pulse electron spin echo envelope modulation (ESEEM) data to quantify the number of water ligands coordinated to the {FeNO}(7) centers was explored. For this aspect of the study, HYSCORE spectra were important for defining a spectral window where empirical integration of ESEEM spectra would be the most accurate.

Constraints on Exotic Dipole-Dipole Couplings between Electrons at the Micrometer Scale

NASA Astrophysics Data System (ADS)

Kotler, Shlomi; Ozeri, Roee; Kimball, Derek F. Jackson

2015-08-01

New constraints on exotic dipole-dipole interactions between electrons at the micrometer scale are established, based on a recent measurement of the magnetic interaction between two trapped 88Sr+ ions. For light bosons (mass≤0.1 eV ) we obtain a 90% confidence interval for an axial-vector-mediated interaction strength of |gAegAe/4 π ℏc | ≤1.2 ×10-17 . Assuming C P T invariance, this constraint is compared to that on anomalous electron-positron interactions, derived from positronium hyperfine spectroscopy. We find that the electron-electron constraint is 6 orders of magnitude more stringent than the electron-positron counterpart. Bounds on pseudoscalar-mediated interaction as well as on torsion gravity are also derived and compared with previous work performed at different length scales. Our constraints benefit from the high controllability of the experimental system which contained only two trapped particles. It therefore suggests a useful new platform for exotic particle searches, complementing other experimental efforts.

Constraints on Exotic Dipole-Dipole Couplings between Electrons at the Micrometer Scale.

PubMed

Kotler, Shlomi; Ozeri, Roee; Kimball, Derek F Jackson

2015-08-21

New constraints on exotic dipole-dipole interactions between electrons at the micrometer scale are established, based on a recent measurement of the magnetic interaction between two trapped 88Sr(+) ions. For light bosons (mass≤0.1  eV) we obtain a 90% confidence interval for an axial-vector-mediated interaction strength of |g(A)(e)g(A)(e)/4πℏc|≤1.2×10(-17). Assuming CPT invariance, this constraint is compared to that on anomalous electron-positron interactions, derived from positronium hyperfine spectroscopy. We find that the electron-electron constraint is 6 orders of magnitude more stringent than the electron-positron counterpart. Bounds on pseudoscalar-mediated interaction as well as on torsion gravity are also derived and compared with previous work performed at different length scales. Our constraints benefit from the high controllability of the experimental system which contained only two trapped particles. It therefore suggests a useful new platform for exotic particle searches, complementing other experimental efforts.

International Conference on Quantum Chemical Calculations of NMR and EPR Parameters Held in Castle Smolenice, Slovak Republic on September 14-18 1998

DTIC Science & Technology

1998-10-21

site. The electric-field- induced linear shift is also observed in the hyperfine splitting of nuclear quadrupole resonance ( NQR ) spectrum of a nucleus...located at a noncentrosymmetric site in a molecule or in crystal lattice. Thus, the linear electric field effect on the ESR and NQR hyperfine splitting...the electric field effects on ESR and NQR hyperfine couplings. Theoretical methods to calculate the electric field effects within Hartree-Fock

Liquid helium-free cryostat and hermetically sealed cryogenic microwave cavity for hyperfine spectroscopy of antiprotonic helium

PubMed Central

Massiczek, O.; Friedreich, S.; Juhász, B.; Widmann, E.; Zmeskal, J.

2011-01-01

The design and properties of a new cryogenic set-up for laser–microwave–laser hyperfine structure spectroscopy of antiprotonic helium – an experiment performed at the CERN-Antiproton Decelerator (AD), Geneva, Switzerland – are described. Similar experiments for 4He have been performed at the AD for several years. Due to the usage of a liquid helium operated cryostat and therefore necessary refilling of coolants, a loss of up to 10% beamtime occurred. The decision was made to change the cooling system to a closed-circuit cryocooler. New hermetically sealed target cells with minimised 3He gas volume and different dimensions of the microwave resonator for measuring the 3He transitions were needed. A new set-up has been designed and tested at Stefan Meyer Institute in Vienna before being used for the 2009 and 2010 beamtimes at the AD. PMID:22267883

Magneto-optical properties of BaCryFe12-yO19 (0.0 ≤ y ≤ 1.0) hexaferrites

NASA Astrophysics Data System (ADS)

Asiri, S.; Güner, S.; Korkmaz, A. D.; Amir, Md.; Batoo, K. M.; Almessiere, M. A.; Gungunes, H.; Sözeri, H.; Baykal, A.

2018-04-01

In this study, nanocrystalline BaCryFe12-yO19 (0.0 ≤ y ≤ 1.0) hexaferrite powders were prepared by sol-gel auto combustion method and the effect of Cr3+ ion substitution on morphology, structure, optic and magnetic properties of Barium hexaferrite were investigated. X-ray powder diffraction (XRD) analyses confirmed the purity of all samples. The XRD data shows that the average crystallite size lies between 60.95 nm and 50.10 nm and same was confirmed by Transmission electron microscopy. Transmission electron and scanning electron microscopy analyses presented the hexagonal morphology of all products. The characteristic hysteresis (σ-H) curves proved the ferromagnetic feature of as grown nanoparticle samples. Specific saturation magnetization (σs) drops from 46.59 to 34.89 emu/g with increasing Cr content while the coercive field values lie between 770 and 1652 Oe. The large magnitude of the magnetocrystalline (intrinsic) anisotropy field, (Ha) between 11.0 and 12.6 kOe proves that all products are magnetically hard. The energy band gap values decrease from 2.0 eV to 1.84 eV with increasing Cr content. From 57Fe Mössbauer spectroscopy, the variation in line width, isomer shift, quadrupole splitting and hyperfine magnetic field values were determined and discussed.

Diverse trends of electron correlation effects for properties with different radial and angular factors in an atomic system: a case study in Ca+

NASA Astrophysics Data System (ADS)

Kumar, Pradeep; Li, Cheng-Bin; Sahoo, B. K.

2018-03-01

Dependencies of electron correlation effects with the rank and radial behavior of spectroscopic properties are analyzed in the singly charged calcium ion (Ca+). To demonstrate these trends, we have determined field shift constants, magnetic dipole and electric quadrupole hyperfine structure constants, Landé g J factors, and electric quadrupole moments that are described by electronic operators with different radial and angular factors. Radial dependencies are investigated by comparing correlation trends among the properties that have similar angular factors and vice versa. To highlight these observations, we present results from the mean-field approach to all-orders along with intermediate contributions. Contributions from higher relativistic corrections are also given. These findings suggest that sometime lower-order approximations can give results agreeing with the experimental results, but inclusion of some of higher-order correlation effects can cause large disagreement with the experimental values. Therefore, validity of a method for accurate evaluation of atomic properties can be tested by performing calculations of several properties simultaneously that have diverse dependencies on the angular and radial factors and comparing with the available experimental results. Nevertheless, it is imperative to include full triple and quadrupole excitations in the all-order many-body methods for high-precision calculations that are yet to be developed adopting spherical coordinate system for atomic studies.

Hyperfine coupling constants of the nitrogen and phosphorus atoms: A challenge for exact-exchange density-functional and post-Hartree-Fock methods

NASA Astrophysics Data System (ADS)

Kaupp, Martin; Arbuznikov, Alexei V.; Heßelmann, Andreas; Görling, Andreas

2010-05-01

The isotropic hyperfine coupling constants of the free N(S4) and P(S4) atoms have been evaluated with high-level post-Hartree-Fock and density-functional methods. The phosphorus hyperfine coupling presents a significant challenge to both types of methods. With large basis sets, MP2 and coupled-cluster singles and doubles calculations give much too small values for the phosphorus atom. Triple excitations are needed in coupled-cluster calculations to achieve reasonable agreement with experiment. None of the standard density functionals reproduce even the correct sign of this hyperfine coupling. Similarly, the computed hyperfine couplings depend crucially on the self-consistent treatment in exact-exchange density-functional theory within the optimized effective potential (OEP) method. Well-balanced auxiliary and orbital basis sets are needed for basis-expansion exact-exchange-only OEP approaches to come close to Hartree-Fock or numerical OEP data. Results from the localized Hartree-Fock and Krieger-Li-Iafrate approximations deviate notably from exact OEP data in spite of very similar total energies. Of the functionals tested, only full exact-exchange methods augmented by a correlation functional gave at least the correct sign of the P(S4) hyperfine coupling but with too low absolute values. The subtle interplay between the spin-polarization contributions of the different core shells has been analyzed, and the influence of even very small changes in the exchange-correlation potential could be identified.

The gamut of alkoxy radicals

NASA Astrophysics Data System (ADS)

Box, Harold C.; Budzinski, Edwin E.; Freund, Harold G.

1984-12-01

It is shown that various radicals exhibiting diverse ESR and ENDOR spectral characteristics are nonetheless a closely related family of alkoxy radicals. The relationship is established by correlating the g tensor with crystal structure and by relating dihedral angles inferred from proton hyperfine couplings to dihedral angles inferred from the g tensor and crystal structure. The analysis also serves to demonstrate that an ESR absorption observed in x-irradiated single crystals of uridine 5'-monophosphate is due to an alkoxy radical.

RADIATIVE TRANSFER MODELING OF THE ENIGMATIC SCATTERING POLARIZATION IN THE SOLAR Na i D{sub 1} LINE

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

Belluzzi, Luca; Bueno, Javier Trujillo; Degl’Innocenti, Egidio Landi

2015-12-01

The modeling of the peculiar scattering polarization signals observed in some diagnostically important solar resonance lines requires the consideration of the detailed spectral structure of the incident radiation field as well as the possibility of ground level polarization, along with the atom's hyperfine structure and quantum interference between hyperfine F-levels pertaining either to the same fine structure J-level, or to different J-levels of the same term. Here we present a theoretical and numerical approach suitable for solving this complex non-LTE radiative transfer problem. This approach is based on the density-matrix metalevel theory (where each level is viewed as a continuousmore » distribution of sublevels) and on accurate formal solvers of the transfer equations and efficient iterative methods. We show an application to the D-lines of Na i, with emphasis on the enigmatic D{sub 1} line, pointing out the observable signatures of the various physical mechanisms considered. We demonstrate that the linear polarization observed in the core of the D{sub 1} line may be explained by the effect that one gets when the detailed spectral structure of the anisotropic radiation responsible for the optical pumping is taken into account. This physical ingredient is capable of introducing significant scattering polarization in the core of the Na i D{sub 1} line without the need for ground-level polarization.« less

Structural and Electronic Properties Study of Colombian Aurifer Soils by Mössbauer Spectroscopy and X-ray Diffraction

NASA Astrophysics Data System (ADS)

Bustos Rodríguez, H.; Rojas Martínez, Y.; Oyola Lozano, D.; Pérez Alcázar, G. A.; Fajardo, M.; Mojica, J.; Molano, Y. J. C.

2005-02-01

In this work a study on gold mineral samples is reported, using optical microscopy, X-ray diffraction (XRD) and Mössbauer spectroscopy (MS). The auriferous samples are from the El Diamante mine, located in Guachavez-Nariño (Colombia) and were prepared by means of polished thin sections. The petrography analysis registered the presence, in different percentages that depend on the sample, of pyrite, quartz, arsenopyirite, sphalerite, chalcopyrite and galena. The XRD analysis confirmed these findings through the calculated cell parameters. One typical Rietveld analysis showed the following weight percent of phases: 85.0% quartz, 14.5% pyrite and 0.5% sphalerite. In this sample, MS demonstrated the presence of two types of pyrite whose hyperfine parameters are δ 1 = 0.280 ± 0.002 mm/s and Δ 1 = 0.642 ± 0.002 mm/s, δ 2 = 0.379 ± 0.002 mm/s and Δ 2 = 0.613 ± 0.002 mm/s.

Free radicals produced by the oxidation of gallic acid: An electron paramagnetic resonance study.

PubMed

Eslami, Angelique C; Pasanphan, Wanvimol; Wagner, Brett A; Buettner, Garry R

2010-08-05

Gallic acid (3,4,5-trihydroxybenzoic acid) is found in a wide variety of plants; it is extensively used in tanning, ink dyes, as well as in the manufacturing of paper. The gallate moiety is a key component of many functional phytochemicals. In this work electron paramagnetic spectroscopy (EPR) was used to detect the free radicals generated by the air-oxidation of gallic acid. We found that gallic acid produces two different radicals as a function of pH. In the pH range between 7-10, the spectrum of the gallate free radical is a doublet of triplets (aH = 1.00 G, aH = 0.23 G, aH = 0.28 G). This is consistent with three hydrogens providing hyperfine splitting. However, in a more alkaline environment, pH >10, the hyperfine splitting pattern transforms into a 1:2:1 pattern (aH (2) = 1.07 G). Using D2O as a solvent, we demonstrate that the third hydrogen (i.e. aH = 0.28 G) at lower pH is a slowly exchanging hydron, participating in hydrogen bonding with two oxygens in ortho position on the gallate ring. The pKa of this proton has been determined to be 10. This simple and novel approach permitted the understanding of the prototropic equilibrium of the semiquinone radicals generated by gallic acid, a ubiquitous compound, allowing new insights into its oxidation and subsequent reactions.

Research on Spectroscopy, Opacity, and Atmospheres

NASA Astrophysics Data System (ADS)

Kurucz, Robert L.

1996-01-01

The main accomplishment was the merging of all the atomic line data into one wavelength-sorted list that is simple to use. We have combined all the atomic files from a CDROM into 534,910 line files GFALL.DAT and GFELEN.DAT. These are the data we use to compute spectra. They are not up to date. References are given in GFALL.REF or GFELEK.REF. There are no references after 1988, and for light elements there are no references after 1979. One new development is the inclusion of hyperfine splitting for the iron group elements using hyperfine data from the literature through 1993. The data are very incomplete. We have supplied a program for splitting the line list for a species. It reads the hyperfine and isotopic splitting parameters for levels and computes the splittings whenever those levels appear. Lines with no splitting data are copied untouched. Because Sc, Mn, and Co are monoisotopic, only the hyperfine splittings are needed. Since 51V is much more abundant than 50V, the isotope shifts are small for 51V, and we approximate V with 51V. GFALLHYP.DAT has 754,946 lines including hyperfine Sc I, V I, Mn I, and Co I.

Single crystal X- and Q-band EPR spectroscopy of a binuclear Mn(2)(III,IV) complex relevant to the oxygen-evolving complex of photosystem II.

PubMed

Yano, Junko; Sauer, Kenneth; Girerd, Jean-Jacques; Yachandra, Vittal K

2004-06-23

The anisotropic g and hyperfine tensors of the Mn di-micro-oxo complex, [Mn(2)(III,IV)O(2)(phen)(4)](PF(6))(3).CH(3)CN, were derived by single-crystal EPR measurements at X- and Q-band frequencies. This is the first simulation of EPR parameters from single-crystal EPR spectra for multinuclear Mn complexes, which are of importance in several metalloenzymes; one of them is the oxygen-evolving complex in photosystem II (PS II). Single-crystal [Mn(2)(III,IV)O(2)(phen)(4)](PF(6))(3).CH(3)CN EPR spectra showed distinct resolved (55)Mn hyperfine lines in all crystal orientations, unlike single-crystal EPR spectra of other Mn(2)(III,IV) di-micro-oxo bridged complexes. We measured the EPR spectra in the crystal ab- and bc-planes, and from these spectra we obtained the EPR spectra of the complex along the unique a-, b-, and c-axes of the crystal. The crystal orientation was determined by X-ray diffraction and single-crystal EXAFS (Extended X-ray Absorption Fine Structure) measurements. In this complex, the three crystallographic axes, a, b, and c, are parallel or nearly parallel to the principal molecular axes of Mn(2)(III,IV)O(2)(phen)(4) as shown in the crystallographic data by Stebler et al. (Inorg. Chem. 1986, 25, 4743). This direct relation together with the resolved hyperfine lines significantly simplified the simulation of single-crystal spectra in the three principal directions due to the reduction of free parameters and, thus, allowed us to define the magnetic g and A tensors of the molecule with a high degree of reliability. These parameters were subsequently used to generate the solution EPR spectra at both X- and Q-bands with excellent agreement. The anisotropic g and hyperfine tensors determined by the simulation of the X- and Q-band single-crystal and solution EPR spectra are as follows: g(x) = 1.9887, g(y) = 1.9957, g(z) = 1.9775, and hyperfine coupling constants are A(III)(x) = |171| G, A(III)(y) = |176| G, A(III)(z) = |129| G, A(IV)(x) = |77| G, A(IV)(y) = |74| G, A(IV)(z) = |80| G.

Absence of exchange interaction between localized magnetic moments and conduction-electrons in diluted Er{sup 3+} gold-nanoparticles

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

Lesseux, G. G., E-mail: lesseux@ifi.unicamp.br; Urbano, R. R.; Iwamoto, W.

2014-05-07

The Electron Spin Resonance (ESR) of diluted Er{sup 3+} magnetic ions in Au nanoparticles (NPs) is reported. The NPs were synthesized by reducing chloro triphenyl-phosphine gold(I) and erbium(III) trifluoroacetate. The Er{sup 3+} g-value along with the observed hyperfine splitting indicate that the Er{sup 3+} impurities are in a local cubic symmetry. Furthermore, the Er{sup 3+} ESR spectra show that the exchange interaction between the 4f and the conduction electrons (ce) is absent or negligible in Au{sub 1–x}Er{sub x} NPs, in contrast to the ESR results in bulk Au{sub 1–x}Er{sub x}. Therefore, the nature of this interaction needs to be reexaminedmore » at the nano scale range.« less

Mechanism of 'GSI oscillations' in electron capture by highly charged hydrogen-like atomic ions

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

Krainov, V. P., E-mail: vpkrainov@mail.ru

2012-07-15

We suggest a qualitative explanation of oscillations in electron capture decays of hydrogen-like {sup 140}Pr and {sup 142}Pm ions observed recently in an ion experimental storage ring (ESR) of Gesellschaft fuer Schwerionenforschung (GSI) mbH, Darmstadt, Germany. This explanation is based on the electron multiphoton Rabi oscillations between two Zeeman states of the hyperfine ground level with the total angular momentum F = 1/2. The Zeeman splitting is produced by a constant magnetic field in the ESR. Transitions between these states are produced by the second, sufficiently strong alternating magnetic field that approximates realistic fields in the GSI ESR. The Zeemanmore » splitting amounts to only about 10{sup -5} eV. This allows explaining the observed quantum beats with the period 7 s.« less

Resistively detected NMR line shapes in a quasi-one-dimensional electron system

NASA Astrophysics Data System (ADS)

Fauzi, M. H.; Singha, A.; Sahdan, M. F.; Takahashi, M.; Sato, K.; Nagase, K.; Muralidharan, B.; Hirayama, Y.

2017-06-01

We observe variation in the resistively detected nuclear magnetic resonance (RDNMR) line shapes in quantum Hall breakdown. The breakdown occurs locally in a gate-defined quantum point contact (QPC) region. Of particular interest is the observation of a dispersive line shape occurring when the bulk two-dimensional electron gas (2DEG) set to νb=2 and the QPC filling factor to the vicinity of νQPC=1 , strikingly resemble the dispersive line shape observed on a 2D quantum Hall state. This previously unobserved line shape in a QPC points to a simultaneous occurrence of two hyperfine-mediated spin flip-flop processes within the QPC. Those events give rise to two different sets of nuclei polarized in the opposite direction and positioned at a separate region with different degrees of electronic spin polarization.

ESR Detection of optical dynamic nuclear polarization in GaAs/Al{sub x}Ga{sub 1-x}As quantum wells at unity filling factor in the quantum Hall effect

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

Vitkalov, Sergey A.; Bowers, C. Russell; Simmons, Jerry A.

2000-02-15

This paper presents a study of the enhancement of the Zeeman energy of two-dimensional (2D) conduction electrons near the {nu}=1 filling factor of the quantum Hall effect by optical dynamic nuclear polarization. The change in the Zeeman energy is determined from the Overhauser shift of the transport detected electron spin resonance in GaAs/Al{sub x}Ga{sub 1-x}As multiquantum wells. In a separate experiment the NMR signal enhancement factor is obtained by radio frequency detected nuclear magnetic resonance under similar conditions in the same sample. These measurements afford an estimation of the hyperfine coupling constant between the nuclei and 2D conduction electrons. (c)more » 2000 The American Physical Society.« less

Reply to ``Comment on `Spin- and charge-ordering in oxygen-vacancy-ordered mixed-valence Sr4Fe4O11 ' ''

NASA Astrophysics Data System (ADS)

Ravindran, P.; Vidya, R.; Fjellvåg, H.; Kjekshus, A.

2008-04-01

Recently, using density-functional theoretical calculations, we have reported [Phys. Rev. B 74, 054422 (2006)] that formal Fe3+ ions reside at the square-pyramidal site and Fe4+ ions in the octahedral site in Sr4Fe4O11 . Based on the interpretation of experimental structural and Mössbauer data from the literature, Adler concludes that our previous first-principles results disagree with experiments on the assignment of oxidation states to Fe in the square-pyramidal and octahedral environments in Sr4Fe4O11 . From a critical examination of the structure data for Sr4Fe4O11 and related oxides with Fe in different oxidation states and theoretically simulated Mössbauer parameters (hyperfine field, isomer shift, and quadrupole splitting), here we show that information on charges residing on the different constituents cannot be directly derived either from experimental structure or Mössbauer data. From additional analyses of the chemical bonding on the basis of charge density, charge transfer, electron localization function, crystal orbital Hamilton population, Born effective charge, and partial density of states, we substantiate our previous assignment of formal Fe3+ and Fe4+ to the square-pyramidal and octahedral sites, respectively, in Sr4Fe4O11 .

Towards fundamental understanding of ultracold KRb

NASA Astrophysics Data System (ADS)

Kotochigova, Svetlana

2009-05-01

The recent formation of ultracold KRb molecules in their absolute rovibrational ground state [1] has created great promise for study of collective phenomena that rely on the long-range interactions between polar molecules. Here we discuss the theoretical analysis of various essential properties of the KRb molecules [2] that accompanied these experimental advances. This analysis is based on multi-channel bound-state calculations of both ground and excited electronic states. We have found that the theoretical hyperfine and Zeeman mixed X^1&+circ; and a^3&+circ; vibrational structure shows excellent agreement with the experimentally observed structure. In addition, multi-channel calculations of the rovibrational structure of the excited state potentials have allowed us to find the optimal transitions to the lowest v=0 vibrational levels. Finally, we examine the dynamic polarizability of vibrationally cold KRb molecules as a function of laser frequency. Based on this knowledge, laser frequencies can be selected to minimize decoherence from loss of molecules due to spontaneous or laser-induced transitions. [1] K.-K. Ni, S. Ospelkaus, M. H. G. de Miranda, A. Peer, B. Neyenhuis, J. J. Zirbel, S. Kotochigova, P. S. Julienne, D. S. Jin, and J. Ye, Science 322, 231 (2008). [2] S. Kotochigova, E. Tiesinga, and P. S. Julienne, submitted to New J. Phys. (2009).

Frequency metrology using highly charged ions

NASA Astrophysics Data System (ADS)

Crespo López-Urrutia, J. R.

2016-06-01

Due to the scaling laws of relativistic fine structure splitting, many forbidden optical transitions appear within the ground state configurations of highly charged ions (HCI). In some hydrogen-like ions, even the hyperfine splitting of the 1s ground state gives rise to optical transitions. Given the very low polarizability of HCI, such laser-accessible transitions are extremely impervious to external perturbations and systematics that limit optical clock performance and arise from AC and DC Stark effects, such as black-body radiation and light shifts. Moreover, AC and DC Zeeman splitting are symmetric due to the much larger relativistic spin-orbit coupling and corresponding fine-structure splitting. Appropriate choice of states or magnetic sub-states with suitable total angular momentum and magnetic quantum numbers can lead to a cancellation of residual quadrupolar shifts. All these properties are very advantageous for the proposed use of HCI forbidden lines as optical frequency standards. Extremely magnified relativistic, quantum electrodynamic, and nuclear size contributions to the binding energies of the optically active electrons make HCI ideal tools for fundamental research, as in proposed studies of a possible time variation of the fine structure constant. Beyond this, HCI that cannot be photoionized by vacuum-ultraviolet photons could also provide frequency standards for future lasers operating in that range.

Coherent coupling between a quantum dot and a donor in silicon

DOE PAGES

Harvey-Collard, Patrick; Jacobson, N. Tobias; Rudolph, Martin; ...

2017-10-18

Individual donors in silicon chips are used as quantum bits with extremely low error rates. However, physical realizations have been limited to one donor because their atomic size causes fabrication challenges. Quantum dot qubits, in contrast, are highly adjustable using electrical gate voltages. This adjustability could be leveraged to deterministically couple donors to quantum dots in arrays of qubits. In this work, we demonstrate the coherent interaction of a 31P donor electron with the electron of a metal-oxide-semiconductor quantum dot. We form a logical qubit encoded in the spin singlet and triplet states of the two-electron system. We show thatmore » the donor nuclear spin drives coherent rotations between the electronic qubit states through the contact hyperfine interaction. This provides every key element for compact two-electron spin qubits requiring only a single dot and no additional magnetic field gradients, as well as a means to interact with the nuclear spin qubit.« less

Torsionally mediated spin-rotation hyperfine splittings at moderate to high J values in methanol

NASA Astrophysics Data System (ADS)

Belov, S. P.; Golubiatnikov, G. Yu.; Lapinov, A. V.; Ilyushin, V. V.; Alekseev, E. A.; Mescheryakov, A. A.; Hougen, J. T.; Xu, Li-Hong

2016-07-01

This paper presents an explanation based on torsionally mediated proton-spin-overall-rotation interaction for the observation of doublet hyperfine splittings in some Lamb-dip sub-millimeter-wave transitions between ground-state torsion-rotation states of E symmetry in methanol. These unexpected doublet splittings, some as large as 70 kHz, were observed for rotational quantum numbers in the range of J = 13 to 34, and K = - 2 to +3. Because they increase nearly linearly with J for a given branch, we confined our search for an explanation to hyperfine operators containing one nuclear-spin angular momentum factor I and one overall-rotation angular momentum factor J (i.e., to spin-rotation operators) and ignored both spin-spin and spin-torsion operators, since they contain no rotational angular momentum operator. Furthermore, since traditional spin-rotation operators did not seem capable of explaining the observed splittings, we constructed totally symmetric "torsionally mediated spin-rotation operators" by multiplying the E-species spin-rotation operator by an E-species torsional-coordinate factor of the form e±niα. The resulting operator is capable of connecting the two components of a degenerate torsion-rotation E state. This has the effect of turning the hyperfine splitting pattern upside down for some nuclear-spin states, which leads to bottom-to-top and top-to-bottom hyperfine selection rules for some transitions, and thus to an explanation for the unexpectedly large observed hyperfine splittings. The constructed operator cannot contribute to hyperfine splittings in the A-species manifold because its matrix elements within the set of torsion-rotation A1 and A2 states are all zero. The theory developed here fits the observed large doublet splittings to a root-mean-square residual of less than 1 kHz and predicts unresolvable splittings for a number of transitions in which no doublet splitting was detected.

Torsionally mediated spin-rotation hyperfine splittings at moderate to high J values in methanol

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

Belov, S. P.; Golubiatnikov, G. Yu.; Lapinov, A. V.

2016-07-14

This paper presents an explanation based on torsionally mediated proton-spin–overall-rotation interaction for the observation of doublet hyperfine splittings in some Lamb-dip sub-millimeter-wave transitions between ground-state torsion-rotation states of E symmetry in methanol. These unexpected doublet splittings, some as large as 70 kHz, were observed for rotational quantum numbers in the range of J = 13 to 34, and K = − 2 to +3. Because they increase nearly linearly with J for a given branch, we confined our search for an explanation to hyperfine operators containing one nuclear-spin angular momentum factor I and one overall-rotation angular momentum factor J (i.e.,more » to spin-rotation operators) and ignored both spin-spin and spin-torsion operators, since they contain no rotational angular momentum operator. Furthermore, since traditional spin-rotation operators did not seem capable of explaining the observed splittings, we constructed totally symmetric “torsionally mediated spin-rotation operators” by multiplying the E-species spin-rotation operator by an E-species torsional-coordinate factor of the form e{sup ±niα}. The resulting operator is capable of connecting the two components of a degenerate torsion-rotation E state. This has the effect of turning the hyperfine splitting pattern upside down for some nuclear-spin states, which leads to bottom-to-top and top-to-bottom hyperfine selection rules for some transitions, and thus to an explanation for the unexpectedly large observed hyperfine splittings. The constructed operator cannot contribute to hyperfine splittings in the A-species manifold because its matrix elements within the set of torsion-rotation A{sub 1} and A{sub 2} states are all zero. The theory developed here fits the observed large doublet splittings to a root-mean-square residual of less than 1 kHz and predicts unresolvable splittings for a number of transitions in which no doublet splitting was detected.« less

Mixing of the lowest-lying qqq configurations with JP =1/2- in different hyperfine interaction models

NASA Astrophysics Data System (ADS)

Chen, Jia; An, Chunsheng; Chen, Hong

2018-02-01

We investigate mixing of the lowest-lying qqq configurations with JP = 1/2- caused by the hyperfine interactions between quarks mediated by Goldstone Boson Exchange, One Gluon Exchange, and both Goldstone Boson and One Gluon exchange, respectively. The first orbitally excited nucleon, Σ, Λ and Ξ states are considered. Contributions of both the contact term and tensor term are taken into account. Our numerical results show that mixing of the studied configurations in the two employed hyperfine interaction models are very different. Therefore, the present results, which should affect the strong and electromagnetic decays of baryon resonances, may be used to examine the present employed hyperfine interaction models. Supported by National Natural Science Foundation of China (11675131,11645002), Chongqing Natural Science Foundation (cstc2015jcyjA00032) and Fundamental Research Funds for the Central Universities (SWU115020)

Ab initio calculations of torsionally mediated hyperfine splittings in E states of acetaldehyde

NASA Astrophysics Data System (ADS)

Xu, Li-Hong; Reid, E. M.; Guislain, B.; Hougen, J. T.; Alekseev, E. A.; Krapivin, I.

2017-12-01

Quantum chemistry packages can be used to predict with reasonable accuracy spin-rotation hyperfine interaction constants for methanol, which contains one methyl-top internal rotor. In this work we use one of these packages to calculate components of the spin-rotation interaction tensor for acetaldehyde. We then use torsion-rotation wavefunctions obtained from a fit to the acetaldehyde torsion-rotation spectrum to calculate the expected magnitude of hyperfine splittings analogous to those observed at relatively high J values in the E symmetry states of methanol. We find that theory does indeed predict doublet splittings at moderate J values in the acetaldehyde torsion-rotation spectrum, which closely resemble those seen in methanol, but that the factor of three decrease in hyperfine spin-rotation constants compared to methanol puts the largest of the acetaldehyde splittings a factor of two below presently available Lamb-dip resolution.

High-resolution internal state control of ultracold 23Na87Rb molecules

NASA Astrophysics Data System (ADS)

Guo, Mingyang; Ye, Xin; He, Junyu; Quéméner, Goulven; Wang, Dajun

2018-02-01

We report the full internal state control of ultracold 23Na87Rb molecules, including vibrational, rotational, and hyperfine degrees of freedom. Starting from a sample of weakly bound Feshbach molecules, we realize the creation of molecules in single hyperfine levels of both the rovibrational ground and excited states with a high-efficiency and high-resolution stimulated Raman adiabatic passage. This capability brings broad possibilities for investigating ultracold polar molecules with different chemical reactivities and interactions with a single molecular species. Moreover, starting from the rovibrational and hyperfine ground state, we achieve rotational and hyperfine control with one- and two-photon microwave spectroscopy to reach levels not accessible by the stimulated Raman transfer. The combination of these two techniques results in complete control over the internal state of ultracold polar molecules, which paves the way to study state-dependent molecular collisions and state-controlled chemical reactions.

Acid-base titration of melanocortin peptides: evidence of Trp rotational conformers interconversion.

PubMed

Fernandez, Roberto M; Vieira, Renata F F; Nakaie, Clóvis R; Lamy, M Teresa; Ito, Amando S

2005-01-01

Tryptophantime-resolved fluorescence was used to monitor acid-base titration properties of alpha-melanocyte stimulating hormone (alpha-MSH) and the biologically more potent analog [Nle4, D-Phe7]alpha -MSH (NDP-MSH), labeled or not with the paramagnetic amino acid probe 2,2,6,6-tetramthylpiperidine-N-oxyl-4-amino-4-carboxylic acid (Toac). Global analysis of fluorescence decay profiles measured in the pH range between 2.0 and 11.0 showed that, for each peptide, the data could be well fitted to three lifetimes whose values remained constant. The less populated short lifetime component changed little with pH and was ascribed to Trp g+ chi1 rotamer, in which electron transfer deactivation predominates over fluorescence. The long and intermediate lifetime preexponential factors interconverted along that pH interval and the result was interpreted as due to interconversion between Trp g- and trans chi1 rotamers, driven by conformational changes promoted by modifications in the ionization state of side-chain residues. The differences in the extent of interconversion in alpha-MSH and NDP-MSH are indicative of structural differences between the peptides, while titration curves suggest structural similarities between each peptide and its Toac-labeled species, in aqueous solution. Though less sensitive than fluorescence, the Toac electron spin resonance (ESR) isotropic hyperfine splitting parameter can also monitor the titration of side-chain residues located relatively far from the probe. Copyright (c) 2005 Wiley Periodicals, Inc.

A Purple Cupredoxin from Nitrosopumilus maritimus Containing a Mononuclear Type 1 Copper Center with an Open Binding Site

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

Hosseinzadeh, Parisa; Tian, Shiliang; Marshall, Nicholas M.

2016-05-25

Mononuclear cupredoxin proteins usually contain a coordinately saturated type 1 copper (T1Cu) center and function exclusively as electron carriers. Here we report a cupredoxin isolated from the nitrifying archaeon Nitrosopumilus maritimus SCM1, called Nmar1307, that contains a T1Cu center with an open binding site containing water. It displays a deep purple color due to strong absorptions around 413 nm (1880 M –1 cm –1) and 558 nm (2290 M –1 cm –1) in the UV–vis electronic spectrum. EPR studies suggest the protein contains two Cu(II) species of nearly equal population, one nearly axial, with hyperfine constant A∥ = 98 ×more » 10 –4 cm –1, and another more rhombic, with a smaller A∥ value of 69 × 10 –4 cm –1. The X-ray crystal structure at 1.6 Å resolution confirms that it contains a Cu atom coordinated by two His and one Cys in a trigonal plane, with an axial H2O at 2.25 Å. Both UV–vis absorption and EPR spectroscopic studies suggest that the Nmar1307 can oxidize NO to nitrite, an activity that is attributable to the high reduction potential (354 mV vs SHE) of the copper site. These results suggest that mononuclear cupredoxins can have a wide range of structural features, including an open binding site containing water, making this class of proteins even more versatile.« less

57Fe Mössbauer study of stoichiometric iron-based superconductor CaKFe 4As 4: a comparison to KFe 2As 2 and CaFe 2As 2

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

Bud’ko, Sergey L.; Kong, Tai; Meier, William R.

57Fe Mössbauer spectra at different temperatures between ~5 and ~300 K were measured on an oriented mosaic of single crystals of CaKFe 4 As 4. The data indicate that is a well formed compound with narrow spectral lines, no traces of other, Fe – containing, secondary phases in the spectra and no static magnetic order. There is no discernible feature at the superconducting transition temperature in any of the hyperfine parameters. The temperature dependence of the quadrupole splitting approximately follows the empirical ‘ T 3/2 law’. Furthermore, the hyperfine parameters of CaKFe 4 As 4 are compared with those formore » measured in this work, and the literature data for CaFe 2 As 2, and were found to be in between those for these two, ordered, 122 compounds, in agreement with the gross view of CaKFe 4 As 4 as a structural analog of KFe 2 As 2 and CaFe 2 As 2 that has alternating Ca- and K-layers in the structure.« less

57Fe Mössbauer study of stoichiometric iron-based superconductor CaKFe 4As 4: a comparison to KFe 2As 2 and CaFe 2As 2

DOE PAGES

Bud’ko, Sergey L.; Kong, Tai; Meier, William R.; ...

2017-07-06

57Fe Mössbauer spectra at different temperatures between ~5 and ~300 K were measured on an oriented mosaic of single crystals of CaKFe 4 As 4. The data indicate that is a well formed compound with narrow spectral lines, no traces of other, Fe – containing, secondary phases in the spectra and no static magnetic order. There is no discernible feature at the superconducting transition temperature in any of the hyperfine parameters. The temperature dependence of the quadrupole splitting approximately follows the empirical ‘ T 3/2 law’. Furthermore, the hyperfine parameters of CaKFe 4 As 4 are compared with those formore » measured in this work, and the literature data for CaFe 2 As 2, and were found to be in between those for these two, ordered, 122 compounds, in agreement with the gross view of CaKFe 4 As 4 as a structural analog of KFe 2 As 2 and CaFe 2 As 2 that has alternating Ca- and K-layers in the structure.« less

Ground state spectrum of methylcyanide

NASA Astrophysics Data System (ADS)

Šimečková, Marie; Urban, Štěpán; Fuchs, Ulrike; Lewen, Frank; Winnewisser, Gisbert; Morino, Isamu; Yamada, Koichi M. T.

2004-08-01

The rotational spectrum of methylcyanide (acetonitrile) in the ground vibrational state was measured in the spectral region from 91 to 810 GHz using the Cologne and Tsukuba spectrometers operated in the Doppler-limited and sub-Doppler saturation layouts. The resolution of the saturation Lamb-dip measurements is estimated to be about 1 kHz at the best of circumstances and the measuring accuracy of 10-60 kHz depending very sensitively on the quality of the spectrum. In the cases of rotational transitions with the low quantum number J ( J<18) and with a low difference of the rotational quantum numbers J- K, the resolved or partly resolved hyperfine structures of the rotational transitions were observed. Together with the most accurate data from the literature, the newly measured experimental data were analyzed using the traditional polynomial energy formula as well as the Padè approximant for the effective rotational Hamiltonian. The resulting rotational, centrifugal distortion, and hyperfine structure spectroscopic constants were obtained with a significantly higher accuracy than the ones listed in the literature. In addition, an anomalous accidental resonance was detected between the K=14 ground state levels and the K=12, + l levels in the excited v8=1 vibrational state.

N-benzoylated 1,4,8,11-tetraazacyclotetradecane and their copper(II) and nickel(II) complexes: Spectral, magnetic, electrochemical, crystal structure, catalytic and antimicrobial studies

NASA Astrophysics Data System (ADS)

Nirmala, G.; Rahiman, A. Kalilur; Sreedaran, S.; Jegadeesh, R.; Raaman, N.; Narayanan, V.

2010-09-01

A series of N-benzoylated cyclam ligands incorporating three different benzoyl groups 1,4,8,11-tetra-(benzoyl)-1,4,8,11-tetraazacyclotetradecane (L 1), 1,4,8,11-tetra-(2-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 2) and 1,4,8,11-tetra-(4-nitrobenzoyl)-1,4,8,11-tetraazacyclotetradecane (L 3) and their nickel(II) and copper(II) complexes are described. Crystal structure of L 1 is also reported. The ligands and complexes were characterized by elemental analysis, electronic, IR, 1H NMR and 13C NMR spectral studies. N-benzoylation causes red shift in the λmax values of the complexes. The cyclic voltammogram of the complexes of ligand L 1 show one-electron, quasi-reversible reduction wave in the region -1.00 to -1.04 V, whereas that of L 2 and L 3 show two quasi-reversible reduction peaks. Nickel complexes show one-electron quasi-reversible oxidation wave at a positive potential in the range +1.05 to +1.15 V. The ESR spectra of the mononuclear copper(II) complexes show four lines, characteristic of square-planar geometry with nuclear hyperfine spin 3/2. All copper(II) complexes show a normal room temperature magnetic moment values μeff 1.70-1.73 BM which is close to the spin-only value of 1.73 BM. Kinetic studies on the oxidation of pyrocatechol to o-quinone using the copper(II) complexes as catalysts and hydrolysis of 4-nitrophenylphosphate using the copper(II) and nickel(II) complexes as catalysts were carried out. All the ligands and their complexes were also screened for antimicrobial activity against Gram-positive, Gram-negative bacteria and human pathogenic fungi.

Electric dipole moment of diatomic molecules by configuration interaction. V - Two states of /2/Sigma/+/ symmetry in CN.

NASA Technical Reports Server (NTRS)

Green, S.

1972-01-01

Previous accurate dipole moment calculation techniques are modified to be applicable to higher excited states of symmetry. The self-consistent fields and configuration interactions are calculated for the X(2)Sigma(+) and B(2)Sigma(+) states of CN. Spin hyperfine constants and spin density at the nucleus are considered in the context of one-electron operator properties. The values of the self-consistent field and configuration interaction for the spin density are compared with experimental values for several diatomic molecules.

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

Davaasuren, Bambar; Dashjav, Enkhtsetseg; Kreiner, Guido

The carboferrates RE{sub 15}[Fe{sub 8}C{sub 25}] (RE=Dy, Ho) were prepared from mixtures of the elements by arc-melting followed with subsequent annealing at 1373 K. The crystal structures were determined from single crystal X-ray diffraction data and revealed an isotypic relationship to Er{sub 15}[Fe{sub 8}C{sub 25}] (hP48, P321). The main feature of the crystal structure is given by Fe{sub 6} cluster units characterized by covalent Fe–Fe bonding interactions. {sup 57}Fe Mössbauer spectra of Dy{sub 15}[Fe{sub 8}C{sub 25}] were fitted by three subspectra with relative spectral weights of about 3:3:2 which is in general agreement with the crystal structure. Below 50 K,more » an onset of magnetic hyperfine fields at the three iron sites is observed which is supposed to be caused by dipolar fields arising from neighboring, slowly relaxing Dy magnetic moments. - Graphical abstract: Fe{sub 6}-cluster in the crystal structure of RE{sub 15}[Fe{sub 8}C{sub 25}], RE=Dy, Ho. - Highlights: • New carboferrates RE{sub 15}[Fe{sub 8}C{sub 25}] with RE=Dy, Ho have been synthesized. • The crystal structures were refined using single crystal X-ray data. • An orientational relationship between Fe{sub 6}-clusters and Fe in γ-Fe is outlined. • {sup 57}Fe Mössbauer spectra are in agreement with structural data from X-rays. • Magnetic hyperfine fields below 50 K are explained by dipolar fields from Dy atoms.« less

A computer program for analyzing unresolved Mossbauer hyperfine spectra

NASA Technical Reports Server (NTRS)

Schiess, J. R.; Singh, J. J.

1978-01-01

The program for analyzing unresolved Mossbauer hyperfine spectra was written in FORTRAN 4 language for the Control Data CYBER 170 series digital computer system with network operating system 1.1. With the present dimensions, the program requires approximately 36,000 octal locations of core storage. A typical case involving two innermost coordination shells in which the amplitudes and the peak positions of all three components were estimated in 25 iterations requires 30 seconds on CYBER 173. The program was applied to determine the effects of various near neighbor impurity shells on hyperfine fields in dilute FeAl alloys.

Spin-orbit-coupled Fermi gases of two-electron ytterbium atoms

NASA Astrophysics Data System (ADS)

He, Chengdong; Song, Bo; Haciyev, Elnur; Ren, Zejian; Seo, Bojeong; Zhang, Shanchao; Liu, Xiong-Jun; Jo, Gyu-Boong

2017-04-01

Spin-orbit coupling (SOC) has been realized in bosonic and fermionic atomic gases opening an avenue to novel physics associated with spin-momentum locking. In this talk, we will demonstrate all-optical method coupling two hyperfine ground states of 173Yb fermions through a narrow optical transition 1S0 -> 3P1. An optical AC Stark shift is applied to split the ground hyperfine levels and separate out an effective spin-1/2 subspace from other spin states for the realization of SOC. The spin dephasing dynamics and the asymmetric momentum distribution of the spin-orbit coupled Fermi gas are observed as a hallmark of SOC. The implementation of all-optical SOC for ytterbium fermions should offer a new route to a long-lived spin-orbit coupled Fermi gas and greatly expand our capability in studying novel spin-orbit physics with alkaline-earth-like atoms. Other ongoing experimental works related to SOC will be also discussed. Funded by Croucher Foundation and Research Grants Council (RGC) of Hong Kong (Project ECS26300014, GRF16300215, GRF16311516, and Croucher Innovation Grants); MOST (Grant No. 2016YFA0301604) and NSFC (No. 11574008).

Effect of boron additions on phase formation and magnetic properties of TbCu7-type melt spun SmFe ribbons

NASA Astrophysics Data System (ADS)

Zheng, Chuanjiang; Yu, Dunbo; Li, Kuoshe; Luo, Yang; Jin, Jinling; Lu, Shuo; Li, Hongwei; Mao, Yongjun; Quan, Ningtao

2016-08-01

Melt spun ribbons of a series of SmFe12Bx (x=0.0, 0.5, 0.75, 1.0, 1.25, and 1.5) have been prepared by the melt spinning technique. Sm-Fe-B melt spun ribbons with single phase TbCu7-type structure were prepared from the SmFe12Bx (x=0.5, 0.75, and 1.0) alloys at the surface velocity around 40 m/s. The addition of boron not only inhibits the appearance of soft magnetic phase α-Fe, but also enhances the ability of amorphous formation for melt spun Sm-Fe ribbons. The concentration of boron atoms, however, exceeds the limit of the solubility (x>1.0) of Sm-Fe alloys, which does not impede the appearance of α-Fe but accelerates the formation of metastable phase Sm2Fe23B3 that is unfavorable to their magnetic properties. Moreover, it is found that the addition of boron whose concentration is 0.0≤x≤0.75 can stabilize the metastable TbCu7-type structure because of the increase of the lattice parameter ratio c/a. The magnetic properties of as-annealed SmFe12B1.0 melt spun ribbons with an energy product of 2.19MGOe, a coercivity of 2.36 kOe and a remanence of 4.8 kGs have been achieved. The microstructural characteristics of as-annealed melt spun SmFe12 and SmFe12B1.0 ribbons have been discussed as well. The following sequence of the hyperfine field H(6l)

Gradient ascent pulse engineering approach to CNOT gates in donor electron spin quantum computing

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

Tsai, D.-B.; Goan, H.-S.

2008-11-07

In this paper, we demonstrate how gradient ascent pulse engineering (GRAPE) optimal control methods can be implemented on donor electron spin qubits in semiconductors with an architecture complementary to the original Kane's proposal. We focus on the high fidelity controlled-NOT (CNOT) gate and we explicitly find the digitized control sequences for a controlled-NOT gate by optimizing its fidelity using the effective, reduced donor electron spin Hamiltonian with external controls over the hyperfine A and exchange J interactions. We then simulate the CNOT-gate sequence with the full spin Hamiltonian and find that it has an error of 10{sup -6} that ismore » below the error threshold of 10{sup -4} required for fault-tolerant quantum computation. Also the CNOT gate operation time of 100 ns is 3 times faster than 297 ns of the proposed global control scheme.« less

Electrical detection of electron-spin-echo envelope modulations in thin-film silicon solar cells

NASA Astrophysics Data System (ADS)

Fehr, M.; Behrends, J.; Haas, S.; Rech, B.; Lips, K.; Schnegg, A.

2011-11-01

Electrically detected electron-spin-echo envelope modulations (ED-ESEEM) were employed to detect hyperfine interactions between nuclear spins and paramagnetic sites, determining spin-dependent transport processes in multilayer thin-film microcrystalline silicon solar cells. Electrical detection in combination with a modified Hahn-echo sequence was used to measure echo modulations induced by 29Si, 31P, and 1H nuclei weakly coupled to electron spins of paramagnetic sites in the amorphous and microcrystalline solar cell layers. In the case of CE centers in the μc-Si:H i-layer, the absence of 1H ESEEM modulations indicates that the adjacencies of CE centers are depleted from hydrogen atoms. On the basis of this result, we discuss several models for the microscopic origin of the CE center and conclusively assign those centers to coherent twin boundaries inside of crystalline grains in μc-Si:H.

The Guanine Cation Radical: Investigation of Deprotonation States by ESR and DFT

PubMed Central

Adhikary, Amitava; Kumar, Anil; Becker, David; Sevilla, Michael D.

2008-01-01

This work reports ESR studies that identify the favored site of deprotonation of the guanine cation radical (G•+) in an aqueous medium at 77 K. Using ESR and UV-visible spectroscopy, one-electron oxidized guanine is investigated in frozen aqueous D2O solutions of 2′-deoxyguanosine (dGuo) at low temperatures at various pHs at which the guanine cation, G•+ (pH 3–5), singly deprotonated species, G(-H)• (pH 7–9) and doubly deprotonated species, G(-2H)•− (pH>11) are found. C-8-deuteration of dGuo to give 8-D-dGuo removes the major proton hyperfine coupling at C-8. This isolates the anisotropic nitrogen couplings for each of the three species and aids our analyses. These anisotropic nitrogen couplings were assigned to specific nitrogen sites by use of 15N substituted derivatives at N1, N2 N3 atoms in dGuo. Both ESR and UV-visible spectra are reported for each of the species: G•+, G(-H)•, and G(-2H)•−. The experimental anisotropic ESR hyperfine couplings are compared to those obtained from DFT calculations for the various tautomers of G(-H)•. Using the B3LYP/6–31G(d) method, the geometries and energies of G•+ and its singly deprotonated state in its two tautomeric forms, G(N1-H)• and G(N2-H)•, were investigated. In a non-hydrated state G(N2-H)• is found to be more stable than G(N1-H)• but on hydration with 7 water molecules G(N1-H)• is found to be more stable than G(N2-H)•. The theoretically calculated hyperfine coupling constants (HFCC) of G•+, G(N1-H)• and G(-2H)•− match the experimentally observed HFCCs best on hydration with 7 or more waters. For G(-2H)•−, the hyperfine coupling constant (HFCC) at the exocyclic nitrogen atom (N2) is especially sensitive to the number of hydrating water molecules; good agreement with experiment is not obtained until 9 or 10 waters of hydration are included. PMID:17125389

Theoretical study of thorium monoxide for the electron electric dipole moment search: electronic properties of H(3)Δ(1) in ThO.

PubMed

Skripnikov, L V; Titov, A V

2015-01-14

Recently, improved limits on the electron electric dipole moment, and dimensionless constant, kT,P, characterizing the strength of the T,P-odd pseudoscalar-scalar electron-nucleus neutral current interaction in the H(3)Δ1 state of ThO molecule were obtained by the ACME collaboration [J. Baron et al., Science 343, 269 (2014)]. The interpretation of the experiment in terms of these fundamental quantities is based on the results of theoretical study of appropriate ThO characteristics, the effective electric field acting on electron, Eeff, and a parameter of the T,P-odd pseudoscalar-scalar interaction, WT,P, given in Skripnikov et al. [J. Chem. Phys. 139, 221103 (2013)] by St. Petersburg group. To reduce the uncertainties of the given limits, we report improved calculations of the molecular state-specific quantities Eeff, 81.5 GV/cm, and WT,P, 112 kHz, with the uncertainty within 7% of the magnitudes. Thus, the values recommended to use for the upper limits of the quantities are 75.8 GV/cm and 104 kHz, correspondingly. The hyperfine structure constant, molecule-frame dipole moment of the H(3)Δ1 state, and the H(3)Δ1 → X(1)Σ(+) transition energy which, in general, can serve as a measure of reliability of the obtained Eeff and WT,P values are also calculated. In addition, we report the first calculation of g-factor for the H(3)Δ1 state of ThO. The results are compared to the earlier experimental and theoretical studies, and a detailed analysis of uncertainties of the calculations is given.

Performance of a GaAlAs laser diode stabilized on a hyperfine component of two-photon transitions in rubidium at 778 nm

NASA Astrophysics Data System (ADS)

Felder, Raymond; Touahri, D.; Acef, Ouali; Hilico, L.; Zondy, Jean-Jacques; Clairon, Andre; de Beauvoir, Beatrice; Biraben, Francois; Julien, Lucile; Nez, Francois; Millerioux, Yves P.

1995-04-01

The absolute frequency measurement of each hyperfine component of the 5S3/2 and 5S5/2 levels in rubidium was done at ENS more than one year ago using Ti-Sa lasers. We built two devices based on diode lasers to study some metrological properties. We measure the frequency differences between hyperfine components of the 5S5/2 level and we calculate the corresponding hyperfine constants. We also measure the frequency interval between the 5S3/2 and 5S5/2 levels using a Schottky diode. The measured stability in terms of Allan variance is 3*10-13t-1/2 up to 2000 s. The light shift is investigated and the difference between our two systems is 1.7 kHz. The repeatability of one system is better than 10-12 and will allow the absolute frequency measurement at this level via the LPTF frequency synthesis chain.

The optical pumping of alkali atoms using coherent radiation from semi-conductor injection lasers and incoherent radiation from resonance lamps

NASA Technical Reports Server (NTRS)

Singh, G.

1973-01-01

An experimental study for creating population differences in the ground states of alkali atoms (Cesium 133) is presented. Studies made on GaAs-junction lasers and the achievement of population inversions among the hyperfine levels in the ground state of Cs 133 by optically pumping it with radiation from a GaAs diode laser. Laser output was used to monitor the populations in the ground state hyperfine levels as well as to perform the hyperfine pumping. A GaAs laser operated at about 77 K was used to scan the 8521 A line of Cs 133. Experiments were performed both with neon-filled and with paraflint-coated cells containing the cesium vapor. Investigations were also made for the development of the triple resonance coherent pulse technique and for the detection of microwave induced hyperfine trasistions by destroying the phase relationships produced by a radio frequency pulse. A pulsed cesium resonance lamp developed, and the lamp showed clean and reproducible switching characteristics.

Influence of Fe-substitution on structural, magnetic and magnetocaloric properties of Nd2Fe17-xCox solid solutions

NASA Astrophysics Data System (ADS)

Bouchaala, N.; Jemmali, M.; Bartoli, T.; Nouri, K.; Hentech, I.; Walha, S.; Bessais, L.; Salah, A. Ben

2018-02-01

Nd2Fe17-xCox (x = 0 , 1 , 2 , 3 , 4) intermetallic compounds, obtained under arc-melting conditions, have been investigated by means of X-ray diffraction analysis (XRD), Mössbauer spectrometry and magnetic measurements. The Rietveld refinement revealed that the sample is a pure compound with rhombohedral Th2Zn17-type structure (R 3 bar m space group) with the following lattice parameters: a = 8.5792 (2) Å, c = 12.4615 (2) Å. Using Mössbauer spectrometry analysis coupled with structural consideration we have unambiguously determined the cobalt atoms preferred inequivalent crystallographic site. Nd2Fe17 show an increase of 3.5 T in their weighted average hyperfine fields upon cobalt substitution. Whatever the cobalt content, the hyperfine field of these compounds follow this sequence Hhf { 6 c } >Hhf { 9 d } >Hhf { 18 f } >Hhf { 18 h }. The magnetic measurements showed that the Curie temperature increases with the Co content. The magnetic entropy change (ΔSM) was estimated from isothermal magnetization curves and it increases from 3.35 J/Kg K for x = 0 to 5.83 J/Kg K for x = 2 at μ0 H = 1.6 T . The relative cooling power (RCP) is in the range of 11.6 J/kg (x = 0) and 16 J/kg (x = 2).

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, Christopher A.; Worden, Earl F.

1995-01-01

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of .sup.167 Er. The hyperfine structure of .sup.167 Er was used to find two three-step photoionization pathways having a common upper energy level.

NUCLEAR CHEMISTRY ANNUAL REPORT 1970

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

Authors, Various

Papers are presented for the following topics: (1) Nuclear Structure and Nuclear Properties - (a) Nuclear Spectroscopy and Radioactivity; (b) Nuclear Reactions and Scattering; (c) Nuclear Theory; and (d) Fission. (2) Chemical and Atomic Physics - (a) Atomic and Molecular Spectroscopy; and (b) Hyperfine Interactions. (3) Physical, Inorganic, and Analytical Chemistry - (a) X-Ray Crystallography; (b) Physical and Inorganic Chemistry; (c) Radiation Chemistry; and (d) Chemical Engineering. (4) Instrumentation and Systems Development.

Theory of the polarization of highly charged ions in storage rings: Production, preservation, observation and application to the search for a violation of the fundamental symmetries

NASA Astrophysics Data System (ADS)

Bondarevskaya, A.; Prozorov, A.; Labzowsky, L.; Plunien, G.; Liesen, D.; Bosch, F.

2011-10-01

Theoretical concepts for the production, preservation and control of polarized highly charged ion beams in storage rings are investigated. It is argued that hydrogen-like ions can be polarized efficiently by optical pumping of the Zeeman sublevels of ground state hyperfine levels and that the maximum achievable nuclear polarization exceeds 90%. In order to study the preservation of the polarization during the ion motion through the magnetic system of the ring, the concept of the instantaneous quantization axis is introduced. It is suggested that the employment of “Siberian snakes” may help to preserve the ion beam polarization in the ring. The control of the beam polarization can be achieved by different methods: by measuring the Stokes parameters for the emitted photons or by observing the angular dependence of the transition rates for polarized ions. The important motivation for the production of polarized ion beams is the possibility to observe parity nonconservation effects in the hyperfine-quenched transitions in helium-like highly charged ions, where these effects can reach an unprecedented high value for atomic physics. The possible observation of parity nonconservation effects connected with the nuclear anapole moment is also discussed. A method for the observation of the electric dipole moment of an electron in a storage ring with a polarized highly charged ion beam is proposed. This method allows, in principle, to improve the existing boundaries for the electric dipole moment of an electron. However, the requirements of the corresponding experiment are very stringent.

An improved approach to identify irradiated spices using electronic nose, FTIR, and EPR spectroscopy.

PubMed

Sanyal, Bhaskar; Ahn, Jae-Jun; Maeng, Jeong-Hwan; Kyung, Hyun-Kyu; Lim, Ha-Kyeong; Sharma, Arun; Kwon, Joong-Ho

2014-09-01

Changes in cumin and chili powder from India resulting from electron-beam irradiation were investigated using 3 analytical methods: electronic nose (E-nose), Fourier transform infrared (FTIR) spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy. The spices had been exposed to 6 to 14 kGy doses recommended for microbial decontamination. E-nose measured a clear difference in flavor patterns of the irradiated spices in comparison with the nonirradiated samples. Principal component analysis further showed a dose-dependent variation. FTIR spectra of the samples showed strong absorption bands at 3425, 3007 to 2854, and 1746 cm(-1). However, both nonirradiated and irradiated spice samples had comparable patterns without any noteworthy changes in functional groups. EPR spectroscopy of the irradiated samples showed a radiation-specific triplet signal at g = 2.006 with a hyper-fine coupling constant of 3 mT confirming the results obtained with the E-nose technique. Thus, E-nose was found to be a potential tool to identify irradiated spices. © 2014 Institute of Food Technologists®

Development of a sensitive setup for laser spectroscopy studies of very exotic calcium isotopes

NASA Astrophysics Data System (ADS)

Garcia Ruiz, R. F.; Gorges, C.; Bissell, M.; Blaum, K.; Gins, W.; Heylen, H.; Koenig, K.; Kaufmann, S.; Kowalska, M.; Krämer, J.; Lievens, P.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Yordanov, D. T.; Yang, X. F.

2017-04-01

An experimental setup for sensitive high-resolution measurements of hyperfine structure spectra of exotic calcium isotopes has been developed and commissioned at the COLLAPS beam line at ISOLDE, CERN. The technique is based on the radioactive detection of decaying isotopes after optical pumping and state selective neutralization (ROC) (Vermeeren et al 1992 Phys. Rev. Lett. 68 1679). The improvements and developments necessary to extend the applicability of the experimental technique to calcium isotopes produced at rates as low as few ions s-1 are discussed. Numerical calculations of laser-ion interaction and ion-beam simulations were explored to obtain the optimum performance of the experimental setup. Among the implemented features are a multi-step optical pumping region for sensitive measurements of isotopes with hyperfine splitting, a high-voltage platform for adequate control of low-energy ion beams and simultaneous β-detection of neutralized and remaining ions. The commissioning of the experimental setup, and the first online results on neutron-rich calcium isotopes are presented.

High-Resolution Rotational Spectrum, Dunham Coefficients, and Potential Energy Function of NaCl.

PubMed

Cabezas, C; Cernicharo, J; Quintana-Lacaci, G; Peña, I; Agundez, M; Prieto, L Velilla; Castro-Carrizo, A; Zuñiga, J; Bastida, A; Alonso, J L; Requena, A

2016-07-13

We report laboratory spectroscopy for the first time of the J = 1-0 and J = 2-1 lines of Na 35 Cl and Na 37 Cl in several vibrational states. The hyperfine structure has been resolved in both transitions for all vibrational levels, which permit us to predict with high accuracy the hyperfine splitting of the rotational transitions of the two isotopologues at higher frequencies. The new data have been merged with all previous works at microwave, millimeter, and infrared wavelengths and fitted to a series of mass-independent Dunham parameters and to a potential energy function. The obtained parameters have been used to compute a new dipole moment function, from which the dipole moment for infrared transitions up to Δ v = 8 has been derived. Frequency and intensity predictions are provided for all rovibrational transitions up to J = 150 and v = 8, from which the ALMA data of evolved stars can be modeled and interpreted.

Monovalent Cation Activation of the Radical SAM Enzyme Pyruvate Formate-Lyase Activating Enzyme.

PubMed

Shisler, Krista A; Hutcheson, Rachel U; Horitani, Masaki; Duschene, Kaitlin S; Crain, Adam V; Byer, Amanda S; Shepard, Eric M; Rasmussen, Ashley; Yang, Jian; Broderick, William E; Vey, Jessica L; Drennan, Catherine L; Hoffman, Brian M; Broderick, Joan B

2017-08-30

Pyruvate formate-lyase activating enzyme (PFL-AE) is a radical S-adenosyl-l-methionine (SAM) enzyme that installs a catalytically essential glycyl radical on pyruvate formate-lyase. We show that PFL-AE binds a catalytically essential monovalent cation at its active site, yet another parallel with B 12 enzymes, and we characterize this cation site by a combination of structural, biochemical, and spectroscopic approaches. Refinement of the PFL-AE crystal structure reveals Na + as the most likely ion present in the solved structures, and pulsed electron nuclear double resonance (ENDOR) demonstrates that the same cation site is occupied by 23 Na in the solution state of the as-isolated enzyme. A SAM carboxylate-oxygen is an M + ligand, and EPR and circular dichroism spectroscopies reveal that both the site occupancy and the identity of the cation perturb the electronic properties of the SAM-chelated iron-sulfur cluster. ENDOR studies of the PFL-AE/[ 13 C-methyl]-SAM complex show that the target sulfonium positioning varies with the cation, while the observation of an isotropic hyperfine coupling to the cation by ENDOR measurements establishes its intimate, SAM-mediated interaction with the cluster. This monovalent cation site controls enzyme activity: (i) PFL-AE in the absence of any simple monovalent cations has little-no activity; and (ii) among monocations, going down Group 1 of the periodic table from Li + to Cs + , PFL-AE activity sharply maximizes at K + , with NH 4 + closely matching the efficacy of K + . PFL-AE is thus a type I M + -activated enzyme whose M + controls reactivity by interactions with the cosubstrate, SAM, which is bound to the catalytic iron-sulfur cluster.

Local moment formation and magnetic coupling of Mn dopants in Bi2Se3: A low-temperature ferromagnetic resonance study

NASA Astrophysics Data System (ADS)

Savchenko, D.; Tarasenko, R.; Vališka, M.; Kopeček, J.; Fekete, L.; Carva, K.; Holý, V.; Springholz, G.; Sechovský, V.; Honolka, J.

2018-05-01

We compare the magnetic and electronic configuration of single Mn atoms in molecular beam epitaxy (MBE) grown Bi2Se3 thin films, focusing on electron paramagnetic (ferromagnetic) resonance (EPR and FMR, respectively) and superconducting quantum interference device (SQUID) techniques. X-ray diffraction (XRD) and electron backscatter diffraction (EBSD) reveal the expected increase of disorder with increasing concentration of magnetic guest atoms, however, Kikuchi patterns show that disorder consists majorly of μm-scale 60° twin domains in the hexagonal Bi2Se3 structure, which are promoted by the presence of single unclustered Mn impurities. Ferromagnetism below TC (5.4±0.3) K can be well described by critical scaling laws M (T) (1 - T /TC) β with a critical exponent β = (0.34 ± 0.2) , suggesting 3D Heisenberg class magnetism instead of e.g. 2D-type coupling between Mn-spins in van der Waals gap sites. From EPR hyperfine structure data we determine a Mn2+ (d5, S = 5/2) electronic configuration with a g-factor of 2.002 for -1/2 → +1/2 transitions. In addition, from the strong dependence of the low temperature FMR fields and linewidth on the field strength and orientation with respect to the Bi2Se3 (0001) plane, we derive magnetic anisotropy energies of up to K1 = -3720 erg/cm3 in MBE-grown Mn-doped Bi2Se3, reflecting the first order magneto-crystalline anisotropy of an in-plane magnetic easy plane in a hexagonal (0001) crystal symmetry. We observe an increase of K1 with increasing Mn concentration, which we interpret to be correlated to a Mn-induced in-plane lattice contraction. Across the ferromagnetic-paramagnetic transition the FMR intensity is suppressed and resonance fields converge the paramagnetic limit of Mn2+ (d5, S = 5/2).

Magnetism and Hyperfine Parameters in Iron Rich Gd_2Fe_{17-x}Si_x Intermetallics

NASA Astrophysics Data System (ADS)

Nouri, K.; Bartoli, T.; Chrobak, A.; Moscovici, J.; Bessais, L.

2018-04-01

Gd_2Fe_{17-x}Si_x (x = 0.25 , 0.5 and 1) samples were synthesized by arc melting and annealed at 1073 K for 1 week. X-ray diffraction analysis by the Rietveld method has shown that these materials crystallize in the rhombohedral Th_2Zn_{17} -type structure (space group R\\bar{3}m ). The Curie temperature increases with Si content x, whereas the unit-cell parameters decrease slightly. The temperature dependence of magnetization data revealed that Gd_2Fe_{17-x}Si_x exhibits a second-order ferromagnetic to paramagnetic phase transition in the vicinity of the Curie temperature. Exchange coupling parameters of R-R, M-M and R-M (R—rare earth, M—transition metal) have been determined from M(T) magnetization curves based on the mean field theory calculation. The magnetic entropy change Δ S_M and the relative cooling power were estimated from isothermal magnetization curves for all samples. In the proximity of {T}_C and in an applied field of 1.56 T, Δ S_M reached a maximum values of 1.38, 1.67 and 3.07 J/kg K for x = 0.25, 0.5 and 1, respectively. We have calculated the magnetic moment per Fe atom from magnetization measurements at 293 K up to 17 kOe, and it decreases with Si content. These results are verified by the Mössbauer spectrometry measurements obtained at the same temperature. The Mössbauer spectra analysis is based on the correlation between the Wigner-Seitz volume and the isomer-shift evolution of each specific site 6c, 9d, 18f, and 18h of the R\\bar{3} m structure. For all Si concentrations, the magnitude of the hyperfine fields are {H_HF}{6c} > {H_HF}{9d} > {H_HF}{18f} > {H_HF}{18h} . The mean hyperfine field decreases with the Si content.

Magnetism and Hyperfine Parameters in Iron Rich Gd_2Fe_{17-x}Si_x Intermetallics

NASA Astrophysics Data System (ADS)

Nouri, K.; Bartoli, T.; Chrobak, A.; Moscovici, J.; Bessais, L.

2018-07-01

Gd_2Fe_{17-x}Si_x (x = 0.25, 0.5 and 1) samples were synthesized by arc melting and annealed at 1073 K for 1 week. X-ray diffraction analysis by the Rietveld method has shown that these materials crystallize in the rhombohedral Th_2Zn_{17}-type structure (space group R\\bar{3}m). The Curie temperature increases with Si content x, whereas the unit-cell parameters decrease slightly. The temperature dependence of magnetization data revealed that Gd_2Fe_{17-x}Si_x exhibits a second-order ferromagnetic to paramagnetic phase transition in the vicinity of the Curie temperature. Exchange coupling parameters of R- R, M- M and R- M ( R—rare earth, M—transition metal) have been determined from M( T) magnetization curves based on the mean field theory calculation. The magnetic entropy change Δ S_M and the relative cooling power were estimated from isothermal magnetization curves for all samples. In the proximity of {T}_C and in an applied field of 1.56 T, Δ S_M reached a maximum values of 1.38, 1.67 and 3.07 J/kg K for x = 0.25, 0.5 and 1, respectively. We have calculated the magnetic moment per Fe atom from magnetization measurements at 293 K up to 17 kOe, and it decreases with Si content. These results are verified by the Mössbauer spectrometry measurements obtained at the same temperature. The Mössbauer spectra analysis is based on the correlation between the Wigner-Seitz volume and the isomer-shift evolution of each specific site 6 c, 9 d, 18 f, and 18 h of the R\\bar{3}m structure. For all Si concentrations, the magnitude of the hyperfine fields are {H_HF}{6c} > {H_HF}{9d} > {H_HF}{18f} > {H_HF}{18h}. The mean hyperfine field decreases with the Si content.

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

Chen, S. L., E-mail: shuch@ist.hokudai.ac.jp; Takayama, J.; Murayama, A.

Time-resolved optical spin orientation spectroscopy was employed to investigate the temperature-dependent electron spin injection in In{sub 0.1}Ga{sub 0.9}As quantum well (QW) and In{sub 0.5}Ga{sub 0.5}As quantum dots (QDs) tunnel-coupled nanostructures with 4, 6, and 8 nm-thick GaAs barriers. The fast picosecond-ranged spin injection from QW to QD excited states (ES) was observed to speed up with temperature, as induced by pronounced longitudinal-optical (LO)-phonon-involved multiple scattering process, which contributes to a thermally stable and almost fully spin-conserving injection within 5–180 K. The LO-phonon coupling was also found to cause accelerated electron spin relaxation of QD ES at elevated temperature, mainly via hyperfine interactionmore » with random nuclear field.« less

Hyperfine-Structure-Induced Depolarization of Impulsively Aligned I2 Molecules

NASA Astrophysics Data System (ADS)

Thomas, Esben F.; Søndergaard, Anders A.; Shepperson, Benjamin; Henriksen, Niels E.; Stapelfeldt, Henrik

2018-04-01

A moderately intense 450 fs laser pulse is used to create rotational wave packets in gas phase I2 molecules. The ensuing time-dependent alignment, measured by Coulomb explosion imaging with a delayed probe pulse, exhibits the characteristic revival structures expected for rotational wave packets but also a complex nonperiodic substructure and decreasing mean alignment not observed before. A quantum mechanical model attributes the phenomena to coupling between the rotational angular momenta and the nuclear spins through the electric quadrupole interaction. The calculated alignment trace agrees very well with the experimental results.

New Tests for Variations of the Fine Structure Constant

NASA Technical Reports Server (NTRS)

Prestage, John D.

1995-01-01

We describe a new test for possible variations of the fine structure constant, by comparisons of rates between clocks based on hyperfine transitions in alkali atomos with different atomic number Z. H- maser, Cs and Hg+ clocks have a different dependence on ia relativistic contributions of order (Z. Recent H-maser vs Hg+ clock comparison data improves laboratory limits on a time variation by 100-fold to giveFuture laser cooled clocks (Be+, Rb, Cs, Hg+, etc.), when compared, will yield the most senstive of all tests for.

Characterization of isolated 1-aza-adamantan-4-one (C9H13NO) from microwave, millimeter-wave and infrared spectroscopy supported by electronic structure calculations

NASA Astrophysics Data System (ADS)

Pirali, O.; Goubet, M.; Boudon, V.; D'Accolti, L.; Fusco, C.; Annese, C.

2017-08-01

We have synthesized 1-aza-adamantan-4-one (C9H13NO) starting from commercial 1,4-cyclohexanedionemonoethylene acetal and tosylmethylisocianide, following a procedure already described in the literature. The high degree of sample purity was demonstrated by gas chromatography and mass spectrometric measurements and its structure evidenced by 1H and 13C NMR spectroscopy. Among numerous interests in physical chemistry, this target molecule is of high relevance for mechanistic evaluation and the synthesis of novel pharmaceutical compounds. We present a thorough spectroscopic study of this molecule by gas phase vibrational and rotational spectroscopy. Accurate vibrational frequencies have been determined from infrared and far-infrared spectra. The pure rotational spectrum of the molecule has been recorded both by cavity-based Fourier transform microwave spectroscopy in the 2-20 GHz region by supersonically expanding the vapor pressure of the warm sample and by room-temperature absorption spectroscopy in the 140-220 GHz range. Accurate sets of rotational and centrifugal distortion parameters of 1-aza-adamantan-4-one in its ground state and in five vibrationally excited states have been derived from these measurements and compared to accurate quantum chemical calculations. The hyperfine parameters have been discussed in terms of molecular structure around the nitrogen quadrupole nucleus.

The NMR contribution to protein-protein networking in Fe-S protein maturation.

PubMed

Banci, Lucia; Camponeschi, Francesca; Ciofi-Baffoni, Simone; Piccioli, Mario

2018-03-22

Iron-sulfur proteins were among the first class of metalloproteins that were actively studied using NMR spectroscopy tailored to paramagnetic systems. The hyperfine shifts, their temperature dependencies and the relaxation rates of nuclei of cluster-bound residues are an efficient fingerprint of the nature and the oxidation state of the Fe-S cluster. NMR significantly contributed to the analysis of the magnetic coupling patterns and to the understanding of the electronic structure occurring in [2Fe-2S], [3Fe-4S] and [4Fe-4S] clusters bound to proteins. After the first NMR structure of a paramagnetic protein was obtained for the reduced E. halophila HiPIP I, many NMR structures were determined for several Fe-S proteins in different oxidation states. It was found that differences in chemical shifts, in patterns of unobserved residues, in internal mobility and in thermodynamic stability are suitable data to map subtle changes between the two different oxidation states of the protein. Recently, the interaction networks responsible for maturing human mitochondrial and cytosolic Fe-S proteins have been largely characterized by combining solution NMR standard experiments with those tailored to paramagnetic systems. We show here the contribution of solution NMR in providing a detailed molecular view of "Fe-S interactomics". This contribution was particularly effective when protein-protein interactions are weak and transient, and thus difficult to be characterized at high resolution with other methodologies.

The millimeter wave spectrum of silver monoxide, AgO

NASA Astrophysics Data System (ADS)

Steimle, T.; Tanimoto, M.; Namiki, K.; Saito, S.

1998-05-01

The pure rotational spectra of 107AgO and 109AgO were recorded in the 117-380 GHz spectral region using a dc-sputtering absorption cell. The 107Ag(I=1/2) and 109Ag(I=1/2) magnetic hyperfine parameters are interpreted in terms of plausible electronic configuration contributions to the X 2Πi state. It is shown that the determined unusual sign of the Λ-doubling and Fermi contact parameters implies that the X 2Πi state is dominated by a three open shell configuration. A comparison with isovalent CuO is made.

Spin Polarization of Rb and Cs n p P2 3/2 (n =5 , 6) Atoms by Circularly Polarized Photoexcitation of a Transient Diatomic Molecule

NASA Astrophysics Data System (ADS)

Mironov, A. E.; Hewitt, J. D.; Eden, J. G.

2017-03-01

We report the selective population of Rb or Cs n p P2 3/2 (n =5 , 6; F =4 , 5) hyperfine states by the photodissociation of a transient, alkali-rare gas diatomic molecule. Circularly polarized (σ-), amplified spontaneous emission (ASE) on the D2 line of Rb or Cs (780.0 and 852.1 nm, respectively) is generated when Rb-Xe or Cs-Xe ground state collision pairs are photoexcited by a σ+-polarized optical field having a wavelength within the D2 blue satellite continuum, associated with the B Σ2 1/2 +←X Σ2 1/2 + (free←free ) transition of the diatomic molecule. The degree of spin polarization of Cs (6 p P3/2 2 ), specifically, is found to be dependent on the interatomic distance (R ) at which the excited complex is born, a result attributed to the structure of the B Σ2 1/2 + state. For Cs-Xe atomic pairs, tuning the wavelength of the optical field from 843 to 848 nm varies the degree of circular polarization of the ASE from 63% to almost unity because of the perturbation, in the 5 ≤R ≤6 Å interval, of the Σ2 1/2 + potential by a d σ molecular orbital associated with a higher Λ 2 electronic state. Monitoring only the Cs 6 p P3/2 2 spin polarization reveals a previously unobserved interaction of CsXe (B Σ2 1/2 + ) with the lowest vibrational levels of a Λ 2 state derived from Cs (5 d )+Xe . By inserting a molecular intermediate into the alkali atom excitation mechanism, these experiments realize electronic spin polarization through populating no more than two n p P2 3/2 hyperfine states, and demonstrate a sensitive spectroscopic probe of R -dependent state-state interactions and their impact on interatomic potentials.

Investigation of Rubidium Hyperfine Structure Frequency Stabilization Mechanisms.

DTIC Science & Technology

1984-08-01

Frueholtz, and C. H. Volk, Phys. Rev. A 27, 1914 (1983). 4. C. Cohen-Tannoudji, Metrologia 13, 161 (1977). 5. W. Happer, and A. C. Tam, Phys. Rev. A 16, 1877...w U C) ED W mF w c M0 -0 Dm U(i2 DOW V) ZivF 00. LA *I U-(JL OLLIAJ - (I 0 7 a I I ~w..-..- ~ * * ~ -~.’,** ~-, .*h4w.’.-* .- ,-~-. . .- * 8

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, C.A.; Worden, E.F.

1995-08-22

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of {sup 167}Er. The hyperfine structure of {sup 167}Er was used to find two three-step photoionization pathways having a common upper energy level. 3 figs.

Abundances of Copper and Zinc in Stars of the Galactic Thin and Thick Disks

NASA Astrophysics Data System (ADS)

Gorbaneva, T. I.; Mishenina, T. V.; Basak, N. Yu.; Soubiran, C.; Kovtyukh, V. V.

The spectra of studied stars were obtained with the ELODIE spectrograph at the 1.93-m telescope of the Observatoire de Haute Provence (France). The determination of Cu and Zn abundances was carried out in LTE assumption by model atmosphere method, for Cu the hyperfine structure was taken into account. Cu and Zn abundance trends for thin and thick disk's stars are presented.

A purple cupredoxin from Nitrosopumilus maritimus containing a mononuclear type 1 copper center with an open binding site

DOE PAGES

Hosseinzadeh, Parisa; Tian, Shiliang; Marshall, Nicholas M.; ...

2016-04-27

Mononuclear cupredoxin proteins usually contain a coordinately saturated type 1 copper (T1Cu) center and function exclusively as electron carriers. Here we report a cupredoxin isolated from the nitrifying archaeon Nitrosopumilus maritimus SCM1, called Nmar1307, that contains a T1Cu center with an open binding site containing water. It displays a deep purple color due to strong absorptions around 413 nm (1880 M –1 cm –1) and 558 nm (2290 M –1 cm –1) in the UV–vis electronic spectrum. EPR studies suggest the protein contains two Cu(II) species of nearly equal population, one nearly axial, with hyperfine constant A ∥ = 98more » × 10 –4 cm –1, and another more rhombic, with a smaller A ∥ value of 69 × 10 –4 cm –1. The X-ray crystal structure at 1.6 Å resolution confirms that it contains a Cu atom coordinated by two His and one Cys in a trigonal plane, with an axial H 2O at 2.25 Å. Both UV–vis absorption and EPR spectroscopic studies suggest that the Nmar1307 can oxidize NO to nitrite, an activity that is attributable to the high reduction potential (354 mV vs SHE) of the copper site. Lastly, these results suggest that mononuclear cupredoxins can have a wide range of structural features, including an open binding site containing water, making this class of proteins even more versatile.« less

Probing the magnetic field dependence of the light hole transition in GaAs/AlGaAs quantum wells using optically pumped NMR

NASA Astrophysics Data System (ADS)

Willmering, Matthew M.; Sesti, Erika L.; Hayes, Sophia E.; Wood, Ryan M.; Bowers, Clifford R.; Thapa, Sunil K.; Stanton, Christopher J.; Reyes, Arneil P.; Kuhns, Philip; McGill, Stephen

2018-02-01

Optically pumped NMR (OPNMR) of the NMR-active Ga/7169 species has been shown to be a unique method to probe electronic energy bands in GaAs, with sensitivity to the light hole-to-conduction band transition. This transition is often obscured in other optical measurements such as magnetoabsorption. Using OPNMR, we exploit the hyperfine interaction between conduction band electrons (and their spin states) and nuclear spins, which are detected through phase-sensitive radio-frequency (NMR) spectroscopy. Measurements were made over a range of external magnetic fields (B0) in two different labs with separate experimental setups to obtain the magnetic field dependence of the light hole-to-conduction band transition energy. In addition, k .p theory was used to interpret the experimental results, mapping out this specific transition's magnetic field dependence in an AlGaAs/GaAs quantum well. The combination of theory and experiment point to a mixing of valence bands at a field of approximately B0=4.7 T, swapping the dominant character of the absorption transition and, thus, explaining the magnetic field dependence. Lastly, the experimental dependence of the light hole-to-conduction band transition energy on B0 is found to be less steep compared to the calculated trend, indicating that inclusion of additional effects may be necessary to accurately model the spin-split band structure. The additional insight gained by Ga/7169 OPNMR about the light hole states will facilitate future testing of more complex band structure models.

Whither HFI/NQI?

NASA Astrophysics Data System (ADS)

Bharuth-Ram, K.

2013-05-01

A brief review is given of the Hyperfine Interactions Conference series and, in particular, of the Joint meetings of the Hyperfine Interactions and Nuclear Quadrupole Interaction (HFI/NQI) Conferences, with respect to number of participants, contributed papers and participant countries. Trends are traced and recommendations are offered to attract a wider participation at future HFI/NQI conferences.

New Nuclear Magnetic Moment of ^{209}Bi: Resolving the Bismuth Hyperfine Puzzle.

PubMed

Skripnikov, Leonid V; Schmidt, Stefan; Ullmann, Johannes; Geppert, Christopher; Kraus, Florian; Kresse, Benjamin; Nörtershäuser, Wilfried; Privalov, Alexei F; Scheibe, Benjamin; Shabaev, Vladimir M; Vogel, Michael; Volotka, Andrey V

2018-03-02

A recent measurement of the hyperfine splitting in the ground state of Li-like ^{208}Bi^{80+} has established a "hyperfine puzzle"-the experimental result exhibits a 7σ deviation from the theoretical prediction [J. Ullmann et al., Nat. Commun. 8, 15484 (2017)NCAOBW2041-172310.1038/ncomms15484; J. P. Karr, Nat. Phys. 13, 533 (2017)NPAHAX1745-247310.1038/nphys4159]. We provide evidence that the discrepancy is caused by an inaccurate value of the tabulated nuclear magnetic moment (μ_{I}) of ^{209}Bi. We perform relativistic density functional theory and relativistic coupled cluster calculations of the shielding constant that should be used to extract the value of μ_{I}(^{209}Bi) and combine it with nuclear magnetic resonance measurements of Bi(NO_{3})_{3} in nitric acid solutions and of the hexafluoridobismuthate(V) BiF_{6}^{-} ion in acetonitrile. The result clearly reveals that μ_{I}(^{209}Bi) is much smaller than the tabulated value used previously. Applying the new magnetic moment shifts the theoretical prediction into agreement with experiment and resolves the hyperfine puzzle.

New Nuclear Magnetic Moment of 209Bi: Resolving the Bismuth Hyperfine Puzzle

NASA Astrophysics Data System (ADS)

Skripnikov, Leonid V.; Schmidt, Stefan; Ullmann, Johannes; Geppert, Christopher; Kraus, Florian; Kresse, Benjamin; Nörtershäuser, Wilfried; Privalov, Alexei F.; Scheibe, Benjamin; Shabaev, Vladimir M.; Vogel, Michael; Volotka, Andrey V.

2018-03-01

A recent measurement of the hyperfine splitting in the ground state of Li-like 80+208Bi has established a "hyperfine puzzle"—the experimental result exhibits a 7 σ deviation from the theoretical prediction [J. Ullmann et al., Nat. Commun. 8, 15484 (2017), 10.1038/ncomms15484; J. P. Karr, Nat. Phys. 13, 533 (2017), 10.1038/nphys4159]. We provide evidence that the discrepancy is caused by an inaccurate value of the tabulated nuclear magnetic moment (μI) of 209Bi. We perform relativistic density functional theory and relativistic coupled cluster calculations of the shielding constant that should be used to extract the value of μI(209ipts>) and combine it with nuclear magnetic resonance measurements of Bi (NO3 )3 in nitric acid solutions and of the hexafluoridobismuthate(V) BiF6- ion in acetonitrile. The result clearly reveals that μI(209Bi) is much smaller than the tabulated value used previously. Applying the new magnetic moment shifts the theoretical prediction into agreement with experiment and resolves the hyperfine puzzle.

ENDOR/ESR of Mn atoms and MnH molecules in solid argon

NASA Astrophysics Data System (ADS)

van Zee, R. J.; Garland, D. A.; Weltner, W., Jr.

1986-09-01

Mn atoms and MnH molecules, the latter formed by reaction between metal and hydrogen atoms, were trapped in solid argon and their ESR/ENDOR spectra measured at 4 K. At each pumping magnetic field two ENDOR lines were observed for 55Mn(I=5/2) atoms, corresponding to hyperfine transitions within the MS =±1/2 levels. Values of the hyperfine interaction constant and nuclear moment of 55Mn were derived from the six sets of data. For MnH, three sets of signals were detected: a proton ``matrix ENDOR'' line, transitions in the MS =0,±1 levels involving MI (55Mn)=1/2, 3/2, 5/2 levels, and proton transitions corresponding to νH and νH±aH. Analysis yielded the hyperfine constant aH =6.8(1) MHz and the nuclear quadrupole coupling constant Q'(55Mn)=-11.81(2) MHz. The latter compared favorably with a theoretical value derived earlier by Bagus and Schaefer. A higher term in the spin Hamiltonian appeared to be necessary to fit the proton hyperfine data.

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

Carvalho, R. S.; Ávila, H. C.; Cremona, M., E-mail: cremona@fis.puc-rio.br

The recently discovered organic magnetoresistance effect (OMAR) reveals the spin-dependent behavior of the charge transport in organic semiconductors. So far, it is known that hyperfine interactions play an important role in this phenomenon and also that spin-orbit coupling is negligible for light-atom based compounds. However, in the presence of heavy atoms, spin-orbit interactions should play an important role in OMAR. It is known that these interactions are responsible for singlet and triplet states mixing via intersystem crossing and the change of spin-charge relaxation time in the charge mobility process. In this work, we report a dramatic change in the OMARmore » effect caused by the presence of strong intramolecular spin-orbit coupling in a series of rare-earth quinolate organic complex-based devices. Our data show a different OMAR lineshape compared with the OMAR lineshape of tris(8-hydroxyquinolinate) aluminum-based devices, which are well described in the literature. In addition, electronic structure calculations based on density functional theory help to establish the connection between this results and the presence of heavy central ions in the different complexes.« less

Prize for a Faculty Member for Research in and Undergraduate Institution: Higher order corrections to positronium energies

NASA Astrophysics Data System (ADS)

Adkins, Gregory

2016-03-01

Positronium spectroscopy is of continuing interest as a high-precision test of our understanding of binding in QED. Positronium-the electron-positron bound state-represents the purest example of binding in QFT as the constituents are structureless and their interactions are dominated by QED with only negligible contributions from strong or weak effects. Positronium differs from other Coulombic bound systems such as hydrogen or muonium in having maximal recoil (the constituent mass ratio m / M is one) and being subject to real and virtual annihilation into photons. Positronium spectroscopy (n = 1 hyperfine splitting, n = 2 fine structure, and the 2 S - 1 S interval) has reached a precision of order 1MHz , and ongoing experimental efforts may lead to improved results. Theoretical calculations of positronium energies at order mα6 ~ 18 . 7MHz are complete, but only partial results are known at order mα7 ~ 0 . 14MHz . I will report on the status of the positronium energy calculations and present new results for order mα7 contributions. Support provided by the NSF through Grant No. PHY-1404268.

EPR imaging and HPLC characterization of the pigment-based organic free radical in black soybean seeds.

PubMed

Nakagawa, Kouichi; Maeda, Hayato

2017-02-01

We investigated the location and distribution of paramagnetic species in dry black, brown, and yellow (normal) soybean seeds using electron paramagnetic resonance (EPR), X-band (9 GHz) EPR imaging (EPRI), and HPLC. EPR primarily detected two paramagnetic species in black soybean. These two different radical species were assigned as stable organic radical and Mn 2+  species based on the g values and hyperfine structures. The signal from the stable radical was noted at g ≈ 2.00 and was relatively strong and stable. Subsequent noninvasive two-dimensional (2D) EPRI of the radical present in black soybean revealed that the stable radical was primarily located in the pigmented region of the soybean coat, with very few radicals observed in the soybean cotyledon (interior). Pigments extracted from black soybean were analyzed using HPLC. The major compound was found to be cyanidin-3-glucoside. Multi-EPR and HPLC results indicate that the stable radical was only found within the pigmented region of the soybean coat, and it could be cyanidin-3-glucoside or an oxidative decomposition product.