Steady state and transient Overhauser effect in systems of three spins

The rate equations describing spin polarization in a system of three spins are derived and solved for the case of a free radical dissolved in a solvent containing two nuclear spins. Triple irradiation experiments indicate that a nuclear spin A can be effectively coupled to an electron spin C via a second nuclear spin B and measurements of both the steady state and transient Overhauser effects are in accord with the theoretical predictions for a three-spin system. The ‘three spin effect’ is found to operate only in dilute solutions of free radicals in which case the probabilities for transitions between different nuclear or electronic energy levels can be determined. It was found to be effective for fluorine nuclei—in the presence of both protons and a free radical and for carbon [13] nuclei in the presence of either protons or fluorine nuclei and a free radical. Detailed measurements have been performed for CHFCl₂, para-difluorobenzene, and meta-fluorotoluene containing the tritertiary butyl phenoxyl radical.     

Quantum gates using electronic and nuclear spins of Yb+ in a magnetic field gradient

An efficient scheme is proposed to carry out gate operations on an array of trapped Yb⁺ ions, based on a previous proposal using both electronic and nuclear degrees of freedom in a magnetic field gradient. For this purpose we consider the Paschen-Back regime (strong magnetic field) and employ a high-field approximation in this treatment. We show the possibility to suppress the unwanted coupling between the electron spins by appropriately swapping states between electronic and nuclear spins. The feasibility of generating the required high magnetic field is discussed.     

Lyman transitions of high rovibrationally excited H2, HD and D2 molecules

Energies and probabilities of Lyman transitions of high rovibrationally excited H₂, HD and D₂ molecules have been measured and compared with calculations. The experimental results are obtained from laser-induced fluorescence spectra that have been recorded in the spectral range from 60 500 to 83 500 cm⁻¹, covering 2/3 of the hydrogen Lyman band system. The necessary vacuum-UV radiation is produced by stimulated anti-Stokes Raman scattering, providing a widely tunable radiation source with narrow spectral bandwidth to resolve single Lyman transitions. The highest internal energies of detected hydrogen isotopologues are close to the dissociation limit. This extends the available data base of Lyman transitions from and to higher rotational states (J > 10) of HD and D₂.     

Born-Oppenheimer breakdown effects and hyperfine structure in the rotational spectra of SbF and SbCl

Pure rotational spectra have been measured for the ground electronic states of SbF and SbCl. The molecules were prepared by laser ablation of Sb metal in the presence of SF₆ or Cl₂, respectively. Their spectra were measured with a cavity pulsed jet Fourier transform microwave spectrometer. Although both molecules have two unpaired electrons, they are subject to Hund’s coupling case (c), and have X₁0⁺ ground states. The spectra have been interpreted with the formalism of ¹Σ⁺ molecules. For both molecules spectra of several isotopomers have been measured in the ground and first excited vibrational states. Large hyperfine splittings attributable to both nuclear quadrupole coupling and nuclear spin-rotation coupling have been observed. A Dunham-type analysis has produced unusually large Born-Oppenheimer breakdown parameters, which are interpreted in terms of the electronic structures of the molecules.     

Dynamic nuclear polarisation via the integrated solid effect II: experiments on naphthalene-h8 doped with pentacene-d14

In dynamic nuclear polarisation (DNP), also called hyperpolarisation, a small amount of unpaired electron spins is added to the sample containing the nuclear spins, and the polarisation of these unpaired electron spins is transferred to the nuclear spins by means of a microwave field. Traditional DNP polarises the electron spin of stable paramagnetic centres by cooling down to low temperature and applying a strong magnetic field. Then weak continuous wave microwave fields are used to induce the polarisation transfer. Complicated cryogenic equipment and strong magnets can be avoided using short-lived photo-excited triplet states that are strongly aligned in the optical excitation process. However, a much faster transfer of the electron spin polarisation is needed and pulsed DNP methods like nuclear orientation via electron spin locking (NOVEL) and the integrated solid effect (ISE) are used.

To describe the polarisation transfer with the strong microwave fields in NOVEL and ISE, the usual perturbation methods cannot be used anymore. In the previous paper, we presented a theoretical approach to calculate the polarisation transfer in ISE. In the present paper, the theory is applied to the system naphthalene-h₈ doped with pentacene-d₁₄ yielding the photo-excited triplet states and compared with experimental results.     

Dynamic nuclear polarisation via the integrated solid effect I: theory

In the hyperpolarisation method known as dynamic nuclear polarisation (DNP), a small amount of unpaired electron spins is added to the sample containing the nuclear spins and the polarisation of these unpaired electron spins is transferred to the nuclear spins by means of a microwave field. Traditional DNP uses weak continuous wave (CW) microwave fields, so perturbation methods can be used to calculate the polarisation transfer. A much faster transfer of the electron spin polarisation is obtained with the integrated solid effect (ISE) which uses strong pulsed microwave fields. As in nuclear orientation via electron spin locking, the polarisation transfer is coherent, similar to the coherence transfer between nuclear spins. This paper presents a theoretical approach to calculate this polarisation transfer.

ISE is successfully used for a fast polarisation transfer from short-lived photo-excited triplet states to the surrounding nuclear spins in molecular crystals. These triplet states are strongly aligned in the photo-excitation process and do not require the low temperatures and strong magnetic fields needed to polarise the electron spins in traditional DNP. In the following paper, the theory is applied to the system naphthalene-h₈ doped with pentacene-d₁₄ which provides the photo-excited triplet states, and compared with experimental results.     

Nuclear magnetic relaxation induced by the relaxation of electron spins

A physical mechanism responsible for the relaxation of nuclear spins coupled by the hyperfine interaction to relaxed electron spins in materials with spin ordering is proposed. The rate of such induced nuclear spin relaxation is proportional to the dynamic shift of the nuclear magnetic resonance (NMR) frequency. Therefore, its maximum effect on the NMR signal should be expected in the case of nuclear spin waves existing in the system. Our estimates demonstrate that the induced relaxation can be much more efficient than that occurring due to the Bloch mechanism. Moreover, there is a qualitative difference between the induced and Bloch relaxations. The dynamics of nuclear spin sublattices under conditions of the induced relaxation is reduced to the rotation of m₁ and m₂ vectors without any changes in their lengths (m ₁ ² (t) = m ₂ ² (t) = m ₀ ² (t)= const). This means that the excitation of NMR signals by the resonant magnetic field does not change the temperature T _n of the nuclear spin system. This is a manifestation of the qualitative difference between the induced and Bloch relaxations. Indeed, for the latter, the increase in T _n accompanying the saturation of NMR signals is the dominant effect.     

Dynamics of diatomic molecules confined in a chemical trap I. Nuclear magnetic resonance experiments on hydrogen in solid C60

A detailed nuclear magnetic resonance analysis of the low-temperature dynamics of hydrogen (H₂, D₂, and HD) trapped in a solid matrix of C₆₀ is presented. Experimental evidence for hindered rotational and localized three-dimensional translational motion for hydrogen within the ‘box’ formed by the C₆₀ molecules is given.     

Recent advances in positive muon spin rotation; muonium as a probe of fullerenes

In non-metallic solids the positive muon often forms paramagnetic muonium centers which are characterized by the hyperfine interactions of the unpaired electron with the positive muon and with the surrounding nuclear spins. The static and fluctuating components of these hyperfine interactions provide information on local molecular dynamics and local electronic structure. Some recent results on C₆₀ and related compounds are presented to illustrate this.     

Effect of paramagnetic impurities on relaxation of nuclear spins in the superconductors

The ratio of nuclear spin relaxations rates R_s/R_n in the superconductors is calculated for different temperatures and concentrations of paramagnetic impurities, on the base of exact formulae for the density of electronic states and the factor of coherence.     

Symmetry considerations for internal rotation in ethylene-like molecules

The theory of the symmetry properties of the rotational and torsional levels is developed for molecules consisting of two identical XY₂ groups connected by a symmetrical linear chain of atoms, with an arbitrary barrier to internal rotation. The levels are classified according to the representations of the double group $\text{G}{}_{16}{}^{\mathrm{(2)}}$ of the Longuet-Higgins permutation-inversion group, and selection rules for electric dipole transitions are derived. It is shown that the symmetries of the normal coordinates of ethylene-like molecules can be different from those given recently by Papou?ek, Sarka, ?pirko and Jordanov. The results are applicable to the vibrational spectra of molecules like B₂F₄ and B₂Cl₄, which have low barriers to internal rotation in their ground states, and to the vibrational and rotational structure of electronic transitions of C₂H₄, where the combining electronic states may have very different torsional potential functions.     

Magnetic Resonance Study of Detonation Nanodiamonds with Surface Chemically Modified by Transition Metal Ions

We report on electron magnetic resonance (EMR) and nuclear magnetic resonance (NMR) study of detonation nanodiamonds (DND) with the surface modified by copper and cobalt ions. The EMR spectrum of the pure DND sample shows an intense singlet originating from broken carbon bonds, while the spectra of copper- and cobalt-modified samples reveal additional signals with g > 2 and pronounced hyperfine structure (for copper). Increase in the Cu/Co concentration causes an increase of the corresponding EMR signals and broadening of the intense carbon-inherited singlet line. Subsequent annealing of the copper-modified samples in a hydrogen gas stream at 550 and 900°C causes narrowing of the singlet line and reduction of the Cu²⁺-related components. Applying the same annealing process to the cobalt-modified samples leads to broadening of the singlet line, reduction of Co²⁺ component and appearance of new intense low-field signals. NMR data correlate well with the EMR findings and yield information on interactions and locations of transition metal ions. ¹³C nuclear spin–lattice relaxation rate R ₁ in pure DND is driven by the interaction of nuclear spins with unpaired electron spins of broken bonds. Chemical modification of the DND surface by Cu and Co causes an increase in the relaxation rate, revealing appearance of paramagnetic Cu²⁺ and Co²⁺ complexes at the DND surface and their interaction with the carbon nuclear spins, both directly and via a coupling of Cu²⁺ and Co²⁺ electrons with those of the broken bonds. The aforementioned annealing of the Cu- and Co-DND results in an inverse process, i.e., a reduction of the relaxation rate, indicating that these complexes are destroyed and metal ions presumably join each other forming copper and cobalt nanoclusters. In the case of Co the nanoclusters are ferromagnetic, which results in the noticeable broadening of the ¹³C NMR lines.     

Quantum computation using the 13C nuclear spins near the single NV defect center in diamond

We discuss the possibility of realizing quantum computation on the basis of a cluster of single interacting nuclear spins in solids. This idea seems to be feasible because of the combination of two techniques—Single Molecule Spectroscopy and Optically Detected Electron Nuclear Double Resonance. Compared to the well-known bulk Nuclear Magnetic Resonance (NMR), the proposed method of quantum computation has the advantage that quantum computation is performed with pure spin states and the quantum processor is more easily scalable. At the same time, the advantages of NMR quantum computation are kept: long coherence time and easy construction of quantum gates. As a specific system to implement the above idea, we discuss the ¹³C-nuclear spins in the nearest vicinity of a single nitrogen-vacancy (NV) defect center in diamond, which can be optically detected using the technique of scanning confocal microscopy. Owing to the hyperfine coupling of the ground state electron paramagnetic spin S=1 of the center to ¹³C nuclear spins in a diamond lattice, the states of nuclear spins in the vicinity of the defect-center can be addressed individually. Preliminary consideration shows that it should be possible to address up to 12 individual ¹³C nuclear spins. The dephasing time of the nuclear spin states at low temperatures allows realization up to 10⁵ gates.     

Raman‐induced Kerr effect spectroscopy of single‐wall carbon nanotubes aqueous suspensions in the range 0.1–10 and 100–250 cm−1

Here, we study a low (less than 0.1 µg/ml) concentration aqueous suspension of single‐wall carbon nanotubes (SWNTs) by Raman‐induced Kerr effect spectroscopy (RIKES) in the spectral bands 0.1–10 and 100–250 cm⁻¹. This method is capable of carrying out direct investigation of SWNT hydration layers. A comparison of RIKES spectra of SWNT aqueous suspension and that of milli‐Q water shows a considerable growth in the intensity of low wavenumber Raman modes. These modes in the 0.1–10 cm⁻¹ range are attributed to the rotational transitions of H₂O₂ and H₂O molecules. We explain the observed intensity increase as due to the production of hydrogen peroxide and the formation of a low‐density depletion layer on the water–nanotube interface. A few SWNT radial breathing modes (RBM)are observed (ω_RBM = 118.5, 164.7 and 233.5 cm⁻¹) in aqueous suspension, which allows us to estimate the SWNT diameters (∼2.0, 1.5, and 1 nm, respectively). Copyright © 2011 John Wiley & Sons, Ltd.     

Rotational contours of electronic and electronic-vibrational bands of carbazole complexes with water cooled in a supersonic jet

The rotational contours of the bands corresponding to electronic and electronic-vibrational transitions of the fluorescence excitation spectrum of jet-cooled carbazole complexes with one, two, and three water molecules have been studied. For the carbazole-(H₂O)₁ complex, two bands with a spectral shift of 0.57 cm^?1 were recorded under exposure to radiation with a spectral width of 0.08 cm^?1 at the frequency of the purely electronic transition and some other electronic-vibrational transitions. This is caused by the tunnel effect. The intensities of the shifted low-frequency bands are threefold weaker than those of high-frequency bands due to different values of nuclear spin-statistical weights. In the carbazole-(H₂O)₂ and carbazole-(H₂O)₃ complexes, water molecules are combined into a chain by the hydrogen bond, and the two ends of the chain are hydrogen-bonded to the carbazole molecule. The principal axes I _A and I _B of the moments of inertia in carbazole-(H₂O)₃ have different orientation compared to the other complexes considered, and this leads to an increase in the intensity of the Q-branch.     

The millimeter and submillimeter spectrum of HO2: The effects of unpaired electronic spin in a light asymmetric rotor

An extensive data set for the transient species HO₂ was acquired in the spectral region between 150 and 550 GHz. The complex spectrum of this light asymmetric rotor with unpaired electronic spin and nuclear hyperfine interactions was analyzed and fit to within experimental uncertainty (<0.1 MHz). This work provides, either by direct measurement or well-founded calculation, a map of the rotational transition frequencies of HO₂ over a wide range of states.     

Quantum spins in Mackay icosahedral gold nanoparticles

We report on the direct observation of the intrinsic magnetization behavior of Mackay icosahedral Au nanoparticles. The spin arrangements in 3.5-nm icosahedral Au particles are found to be ferrimagnetic-like, where the core and surface moments point in opposite directions, with a net spontaneous magnetic moment of 16 μ_B per particle. The unpaired spins behave as J = 1/2 quantum spins. The average level separation is found to be a factor of ~1.53 larger than that estimated according to the Kubo formula for spherical Au particles. This reflects the fact that there are considerably fewer atoms packed in a particle with an icosahedral geometry than with a spherical one.     

Magnetic properties of nanographite with modified zigzag edges

Newly proposed aromatic molecules and graphene fragments are shown to have the high-spin ground state by the first-principles electronic structure calculations. Our strategy to predict magnetic carbon materials is based on our previous conclusion that mono-hydrogenated, di-hydrogenated or mono-fluorinated zigzag edges of honeycomb networks are magnetic. Structural optimization as well as determination of the electronic states was performed for various nanographite ribbons and high-spin molecules, e.g. 1,8,9-di-hydro-anthracene, C₁₉H₁₄ and C₁₄F₁₃. For hydrogenated molecules and ribbons, the total spin S determined by the LSDA calculation coincides with the value expected from a counting rule for the total spin on a bipartite network. However, S depends on structures of fluorinated nanographite.     

EPR measurements of weak exchange interactions coupling unpaired spins in model compounds

I review electron paramagnetic resonance (EPR) measurements performed to evaluate very weak exchange interactions (defined as ?_ex(i, j) = ?J _ij S _i S _j , with 10^?3 cm^?1<|J _ij|<1 cm^?1) between unpaired spins, transmitted through long and weak chemical pathways typical of protein structures. They are performed in appropriate model compounds, mainly copper derivatives of amino acids and peptides, making use of the phenomenon of exchange narrowing and collapse of the resonances. I describe the theoretical basis and the implementations of the method to different situations, including selected experimental values of the exchange couplingsJ between metal centers, and briefly discuss correlations betweenJ and the structure of the paths. Results obtained in relatively simple EPR experiments performed at room temperature in single-crystal samples are compared with those obtained from thermodynamic magnetic measurements having higher experimental difficulties. The experimental information allows describing the role of molecular segments typical of biomolecules (H bonds, aromatic ring stacking, cation-π contacts, etc.) in the transmission of the exchange interaction. The values ofJ obtained in some model compounds are compared with those obtained in proteins to conclude that the magnitudes of the exchange interactions are useful to characterize long and weak biologically relevant chemical pathways. One observes that these exchange couplings are weakly dependent on the nature of the unpaired spins and strongly dependent on the chemical pathway. Thus, measurements of exchange couplings in model compounds may provide useful information about biological function, particularly about electron transfer in proteins.