Long-lived heteronuclear spin-singlet states in liquids at a zero magnetic field.

We report an observation of long-lived spin-singlet states in a 13C-1H spin pair in a zero magnetic field. In 13C-labeled formic acid, we observe spin-singlet lifetimes as long as 37 s, about a factor of 3 longer than the T1 lifetime of dipole polarization in the triplet state. In contrast to common high-field experiments, the observed coherence is a singlet-triplet coherence with a lifetime T2 longer than the T1 lifetime of dipole polarization in the triplet manifold. Moreover, we demonstrate that heteronuclear singlet states formed between a 1H and a 13C nucleus can exhibit longer lifetimes than the respective triplet states even in the presence of additional spins that couple to the spin pair of interest. Although long-lived homonuclear spin-singlet states have been extensively studied, this is the first experimental observation of analogous singlet states in heteronuclear spin pairs.

Constraints on short-range spin-dependent interactions from scalar spin-spin coupling in deuterated molecular hydrogen.

A comparison between existing nuclear magnetic resonance measurements and calculations of the scalar spin-spin interaction (J coupling) in deuterated molecular hydrogen yields stringent constraints on anomalous spin-dependent potentials between nucleons at the atomic scale (∼ 1 Å). The dimensionless coupling constant g(P)(p)g(P)(N)/4 π associated with the exchange of pseudoscalar (axionlike) bosons between nucleons is constrained to be less than 3.6 × 10(-7) for boson masses in the range of 5 keV, representing improvement by a factor of 100 over previous constraints. The dimensionless coupling constant g(A)(p)g(A)(N)/4 π associated with the exchange of an axial-vector boson between nucleons is constrained to be g(A)(p)g(A)(N)/4 π<1.3 × 10(-19) for bosons of mass ≲ 1000 eV, improving constraints at this distance scale by a factor of 100 for proton-proton couplings and more than 8 orders of magnitude for neutron-proton couplings.

Detecting domain walls of axionlike models using terrestrial experiments.

Stable topological defects of light (pseudo)scalar fields can contribute to the Universe's dark energy and dark matter. Currently, the combination of gravitational and cosmological constraints provides the best limits on such a possibility. We take an example of domain walls generated by an axionlike field with a coupling to the spins of standard-model particles and show that, if the galactic environment contains a network of such walls, terrestrial experiments aimed at the detection of wall-crossing events are realistic. In particular, a geographically separated but time-synchronized network of sensitive atomic magnetometers can detect a wall crossing and probe a range of model parameters currently unconstrained by astrophysical observations and gravitational experiments.

Liquid-state nuclear spin comagnetometers.

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

Near-zero-field nuclear magnetic resonance.

We investigate nuclear magnetic resonance (NMR) in near zero field, where the Zeeman interaction can be treated as a perturbation to the electron mediated scalar interaction (J coupling). This is in stark contrast to the high-field case, where heteronuclear J couplings are normally treated as a small perturbation. We show that the presence of very small magnetic fields results in splitting of the zero-field NMR lines, imparting considerable additional information to the pure zero-field spectra. Experimental results are in good agreement with first-order perturbation theory and with full numerical simulation when perturbation theory breaks down. We present simple rules for understanding the splitting patterns in near-zero-field NMR, which can be applied to molecules with nontrivial spectra.

Zero-field remote detection of NMR with a microfabricated atomic magnetometer.

We demonstrate remote detection of nuclear magnetic resonance (NMR) with a microchip sensor consisting of a microfluidic channel and a microfabricated vapor cell (the heart of an atomic magnetometer). Detection occurs at zero magnetic field, which allows operation of the magnetometer in the spin-exchange relaxation-free (SERF) regime and increases the proximity of sensor and sample by eliminating the need for a solenoid to create a leading field. We achieve pulsed NMR linewidths of 26 Hz, limited, we believe, by the residence time and flow dispersion in the encoding region. In a fully optimized system, we estimate that for 1 s of integration, 7 x 10(13) protons in a volume of 1 mm(3), prepolarized in a 10-kG field, can be detected with a signal-to-noise ratio of approximately 3. This level of sensitivity is competitive with that demonstrated by microcoils in 100-kG magnetic fields, without requiring superconducting magnets.

Remote detection of nuclear magnetic resonance with an anisotropic magnetoresistive sensor.

We report the detection of nuclear magnetic resonance (NMR) using an anisotropic magnetoresistive (AMR) sensor. A "remote-detection" arrangement was used in which protons in flowing water were prepolarized in the field of a superconducting NMR magnet, adiabatically inverted, and subsequently detected with an AMR sensor situated downstream from the magnet and the adiabatic inverter. AMR sensing is well suited for NMR detection in microfluidic "lab-on-a-chip" applications because the sensors are small, typically on the order of 10 mum. An estimate of the sensitivity for an optimized system indicates that approximately 6 x 10(13) protons in a volume of 1,000 mum(3), prepolarized in a 10-kG magnetic field, can be detected with a signal-to-noise ratio of 3 in a 1-Hz bandwidth. This level of sensitivity is competitive with that demonstrated by microcoils in superconducting magnets and with the projected sensitivity of microfabricated atomic magnetometers.

Polarized alkali-metal vapor with minute-long transverse spin-relaxation time.

We demonstrate lifetimes of Zeeman populations and coherences in excess of 60 sec in alkali-metal vapor cells with inner walls coated with an alkene material. This represents 2 orders of magnitude improvement over the best paraffin coatings. We explore the temperature dependence of cells coated with this material and investigate spin-exchange relaxation-free magnetometry in a room-temperature environment, a regime previously inaccessible with conventional coating materials.

Temperature dependence of the nitrogen-vacancy magnetic resonance in diamond.

The temperature dependence of the magnetic-resonance spectra of nitrogen-vacancy (NV-) ensembles in the range of 280-330 K was studied. Four samples prepared under different conditions were analyzed with NV- concentrations ranging from 10 ppb to 15 ppm. For all samples, the axial zero-field splitting (ZFS) parameter D was found to vary significantly with temperature, T, as dD/dT=-74.2(7) kHz/K. The transverse ZFS parameter E was nonzero (between 4 and 11 MHz) in all samples, and exhibited a temperature dependence of dE/(EdT)=-1.4(3)x10{-4} K-1. The results might be accounted for by considering local thermal expansion. The temperature dependence of the ZFS parameters presents a significant challenge for diamond magnetometers and may ultimately limit their bandwidth and sensitivity.

Production and detection of atomic hexadecapole at Earth's magnetic field.

Optical magnetometers measure magnetic fields with extremely high precision and without cryogenics. However, at geomagnetic fields, important for applications from landmine removal to archaeology, they suffer from nonlinear Zeeman splitting, leading to systematic dependence on sensor orientation. We present experimental results on a method of eliminating this systematic error, using the hexadecapole atomic polarization moment. In particular, we demonstrate selective production of the atomic hexadecapole moment at Earth's magnetic field and verify its immunity to nonlinear Zeeman splitting. This technique promises to eliminate directional errors in all-optical atomic magnetometers, potentially improving their measurement accuracy by several orders of magnitude.

Zero-field nuclear magnetic resonance spectroscopy of viscous liquids.

We report zero-field NMR measurements of a viscous organic liquid, ethylene glycol. Zero-field spectra were taken showing resolved scalar spin-spin coupling (J-coupling) for ethylene glycol at different temperatures and water contents. Molecular dynamics strongly affects the resonance linewidth, which closely follows viscosity. Quantum chemical calculations have been used to obtain the relative stability and coupling constants of all ethylene glycol conformers. The results show the potential of zero-field NMR as a probe of molecular structure and dynamics in a wide range of environments, including viscous fluids.

Small-sized dichroic atomic vapor laser lock.

Two, lightweight diode laser frequency stabilization systems designed for experiments in the field are described. A significant reduction in size and weight in both models supports the further miniaturization of measurement devices in the field. Similar to a previous design, magnetic field lines are contained within a magnetic shield enclosing permanent magnets and a Rb cell, so that these dichroic atomic vapor laser lock (DAVLL) systems may be used for magnetically sensitive instruments. The mini-DAVLL system (49 mm long) uses a vapor cell (20 mm long) and does not require cell heaters. An even smaller micro-DAVLL system (9 mm long) uses a microfabricated cell (3 mm square) and requires heaters. These new systems show no degradation in performance with regard to previous designs while considerably reducing dimensions.

Note: Detection of a single cobalt microparticle with a microfabricated atomic magnetometer.

We present magnetic detection of a single, 2 µm diameter cobalt microparticle using an atomic magnetometer based on a microfabricated vapor cell. These results represent an improvement by a factor of 10(5) in terms of the detected magnetic moment over previous work using atomic magnetometers to detect magnetic microparticles. The improved sensitivity is due largely to the use of small vapor cells. In an optimized setup, we predict detection limits of 0.17 µm(3).

Optical detection of NMR J-spectra at zero magnetic field.

Scalar couplings of the form JI(1) x I(2) between nuclei impart valuable information about molecular structure to nuclear magnetic-resonance spectra. Here we demonstrate direct detection of J-spectra due to both heteronuclear and homonuclear J-coupling in a zero-field environment where the Zeeman interaction is completely absent. We show that characteristic functional groups exhibit distinct spectra with straightforward interpretation for chemical identification. Detection is performed with a microfabricated optical atomic magnetometer, providing high sensitivity to samples of microliter volumes. We obtain 0.1 Hz linewidths and measure scalar-coupling parameters with 4-mHz statistical uncertainty. We anticipate that the technique described here will provide a new modality for high-precision "J spectroscopy" using small samples on microchip devices for multiplexed screening, assaying, and sample identification in chemistry and biomedicine.

Nonlinear amplification of small spin precession using long-range dipolar interactions.

In measurements of small signals using spin precession the precession angle usually grows linearly in time. We show that a dynamic instability caused by spin interactions can lead to an exponentially growing spin-precession angle, amplifying small signals and raising them above the noise level of a detection system. We demonstrate amplification by a factor of greater than 8 of a spin-precession signal due to a small magnetic field gradient in a spherical cell filled with hyperpolarized liquid 129Xe. This technique can improve the sensitivity in many measurements that are limited by the noise of the detection system, rather than the fundamental spin-projection noise.

Transverse spin relaxation in liquid 129Xe in the presence of large dipolar fields.

Using spin-echo NMR techniques we study the transverse spin relaxation of hyperpolarized liquid 129Xe in a spherical cell. We observe an instability of the transverse magnetization due to dipolar fields produced by liquid 129Xe, and find that imperfections in the pi pulses of the spin-echo sequence suppress this instability. A simple perturbative model of this effect is in good agreement with the data. We obtain a transverse spin relaxation time of 1300 sec in liquid 129Xe, and discuss applications of hyperpolarized liquid 129Xe as a sensitive magnetic gradiometer and for a permanent electric dipole moment search.

Nonlinear effects from dipolar interactions in hyperpolarized liquid 129Xe.

We investigate nonlinear effects of long-range dipolar interactions in a spherical sample of hyperpolarized liquid 129Xe. Using two high-T(c) SQUID detectors we directly measure the evolution of the magnetization gradients. For small initial rf tip angles we observe an increase in the transverse relaxation time T2* by a factor of 5 and coherent oscillations of magnetization gradients. For large tip angles we observe an exponential growth of the magnetization gradients and demonstrate a gain in sensitivity to magnetic field gradients by a factor of 10. Our results are in quantitative agreement with simple analytical predictions. We discuss applications of these nonlinear effects for precision measurements.

Enhancement of SQUID-detected NMR signals with hyperpolarized liquid 129Xe in a 1 microT magnetic field.

We report an enhancement of proton NMR signals by a factor of 10(6) by cross polarization with hyperpolarized liquid 129Xe in an ultralow magnetic field of 1 microT. The NMR signals from cyclopentane, acetone, and methanol are detected using a commercial high-T(c) SQUID magnetometer with a signal-to-noise ratio of up to 1000 from a single 90 degrees tipping pulse. This technique allows a wide range of low-field NMR measurements and is promising for the detection of intermolecular scalar spin-spin couplings. Scalar intermolecular couplings can produce a shift of the average NMR frequency in a hyperpolarized sample even in the presence of rapid chemical exchange.

Numerical and experimental studies of long-range magnetic dipolar interactions.

We describe several numerical methods developed to analyze the behavior of spin polarized liquids in the presence of long-range magnetic dipolar interactions and external field gradients. Two of the methods use a discrete lattice of spins. In the first we calculate the magnetic field from the lattice of spins directly, either in the rotating frame, or in the lab frame. In the second method we include the dipolar fields from linear magnetization gradients analytically and calculate the dipolar fields from higher order gradients in Fourier space, where they are a local function of the magnetization. In the third method the magnetization is expanded in a Taylor series and the dipolar fields are calculated analytically for each term. The results of these calculations are compared to experimental data, in which we use two superconducting quantum interference device magnetometers adjacent to a spherical sample of hyperpolarized liquid 129Xe to detect the evolution of magnetization gradients. In particular, we observe an increase by a factor of 100 of the spin dephasing time in a longitudinal magnetic field gradient due to dipolar interactions of the spins. While each of the numerical techniques has certain limitations, they are generally in agreement with each other and with experimental data.