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John W. Blanchard

Publications and source records attributed to John W. Blanchard.

At least 37 records · Page 2Linked to original sources

Hyperpolarized solution-state NMR spectroscopy with optically polarized crystals

Nuclear spin hyperpolarization provides a promising route to overcome the challenges imposed by the limited sensitivity of nuclear magnetic resonance. Here we demonstrate that dissolution of spin-polarized pentacene-doped naphthalene crystals enables transfer of polarization to target molecules via intermolecular cross relaxation at room temperature and moderate magnetic fields (1.45$\,$T). This makes it possible to exploit the high spin polarization of optically polarized crystals while mitigating the challenges of its transfer to external nuclei, particularly of the large distances and prohibitively weak coupling between source and target nuclei across solid-solid or solid-liquid interfaces. With this method, here we inject the highly polarized mixture into a benchtop NMR spectrometer and observe the polarization dynamics for target $^1$H nuclei. Although the spectra are radiation damped due to the high naphthalene magnetization, we describe a procedure to process the data in order to obtain more conventional NMR spectra, and extract the target nuclei polarization. With the entire process occurring on a timescale of one minute, we observe NMR signals enhanced by factors between -200 and -1730 at 1.45$\,$T for a range of small molecules.

physics.chem-ph↗

Search for axion-like dark matter using solid-state nuclear magnetic resonance

We report the results of an experimental search for ultralight axion-like dark matter in the mass range 162 neV to 166 neV. The detection scheme of our Cosmic Axion Spin Precession Experiment (CASPEr) is based on a precision measurement of $^{207}$Pb solid-state nuclear magnetic resonance in a polarized ferroelectric crystal. Axion-like dark matter can exert an oscillating torque on $^{207}$Pb nuclear spins via the electric-dipole moment coupling $g_d$, or via the gradient coupling $g_{\text{aNN}}$. We calibrated the detector and characterized the excitation spectrum and relaxation parameters of the nuclear spin ensemble with pulsed magnetic resonance measurements in a 4.4 T magnetic field. We swept the magnetic field near this value and searched for axion-like dark matter with Compton frequency within a 1 MHz band centered at 39.65 MHz. Our measurements place the upper bounds $|g_d|<9.5\times10^{-4}\,\text{GeV}^{-2}$ and $|g_{\text{aNN}}|<2.8\times10^{-1}\,\text{GeV}^{-1}$ (95% confidence level) in this frequency range. The constraint on $g_d$ corresponds to an upper bound of $1.0\times 10^{-21}\,\text{e}\cdot\text{cm}$ on the amplitude of oscillations of the neutron electric dipole moment, and $4.3\times 10^{-6}$ on the amplitude of oscillations of CP-violating $θ$ parameter of quantum chromodynamics. Our results demonstrate the feasibility of using solid-state nuclear magnetic resonance to search for axion-like dark matter in the nano-electronvolt mass range.

hep-ex↗

Quantum sensitivity limits of nuclear magnetic resonance experiments searching for new fundamental physics

Nuclear magnetic resonance is a promising experimental approach to search for ultra-light axion-like dark matter. Searches such as the cosmic axion spin-precession experiments (CASPEr) are ultimately limited by quantum-mechanical noise sources, in particular, spin-projection noise. We discuss how such fundamental limits can potentially be reached. We consider a circuit model of a magnetic resonance experiment and quantify three noise sources: spin-projection noise, thermal noise, and amplifier noise. Calculation of the total noise spectrum takes into account the modification of the circuit impedance by the presence of nuclear spins, as well as the circuit back-action on the spin ensemble. Suppression of the circuit back-action is especially important in order for the spin-projection noise limits of searches for axion-like dark matter to reach the quantum chromodynamic axion sensitivity.

quant-ph↗

Photochemically induced dynamic nuclear polarization of heteronuclear singlet order

Photochemically induced dynamic nuclear polarization (photo-CIDNP) is a method to hyperpolarize nuclear spins using light. In most cases, CIDNP experiments are performed at a high magnetic field and the sample is irradiated by the light inside a nuclear magnetic resonance (NMR) spectrometer. Here we demonstrate photo-CIDNP hyperpolarization generated in the Earth magnetic field and under zero- to ultralow field (ZULF) conditions. Irradiating a sample for several seconds with inexpensive light-emitting diodes produces a strong hyperpolarization of 1H and 13C nuclear spins enhancing the NMR signals several hundred times. The hyperpolarized spin states at the Earth field and in ZULF are different. In the latter case, the state corresponds to the singlet order between scalar-coupled 1H-13C nuclear spins. This state has a longer lifetime than the state hyperpolarized at Earth field. The method is simple and cost-efficient and should be applicable to many molecular systems known to exhibit photo-CIDNP, including amino acids and nucleotides.

physics.chem-ph↗

Correlation of high-field and zero- to ultralow-field NMR properties using 2D spectroscopy

The field of zero- to ultralow-field (ZULF) nuclear magnetic resonance (NMR) is currently experiencing a rapid growth, owing to the progress in optical magnetometry, and also attractive features of ZULF NMR, such as low hardware cost and excellent spectral resolution achieved under ZULF conditions. In this work, an approach is proposed and demonstrated for simultaneous acquisition of ZULF-NMR spectra of individual 13C-containing isotopomers of chemical compounds in a complex mixture. The method makes use of fast field cycling, so that the spin evolution takes place at ZULF conditions, whereas signal detection is performed in a high-field NMR spectrometer. This method has excellent sensitivity, also allowing easy assignment of ZULF-NMR spectra to specific analytes in the mixture. We demonstrate that the spectral information is the same as that given by ZULF-NMR, which makes the method suitable for creating a library of ZULF-NMR spectra of various compounds and their isotopomers. The results of the field-cycling experiments can be presented in a convenient way as 2D-NMR spectra with the direct detection giving the high-field 13C-NMR spectrum (carrying the chemical-shift information) and the indirect dimension giving the ZULF-NMR spectrum (containing information about proton-carbon J-couplings). Hence, the method can be seen as a variant of heteronuclear J-resolved spectroscopy, one of the first 2D-NMR techniques.

physics.chem-ph↗

Stochastic fluctuations of bosonic dark matter

Numerous theories extending beyond the standard model of particle physics predict the existence of bosons that could constitute the dark matter (DM) permeating the universe. In the standard halo model (SHM) of galactic dark matter the velocity distribution of the bosonic DM field defines a characteristic coherence time $τ_c$. Until recently, laboratory experiments searching for bosonic DM fields have been in the regime where the measurement time $T$ significantly exceeds $τ_c$, so null results have been interpreted as constraints on the coupling of bosonic DM to standard model particles with a bosonic DM field amplitude $Φ_0$ fixed by the average local DM density. However, motivated by new theoretical developments, a number of recent searches probe the regime where $T\llτ_c$. Here we show that experiments operating in this regime do not sample the full distribution of bosonic DM field amplitudes and therefore it is incorrect to assume a fixed value of $Φ_0$ when inferring constraints on the coupling strength of bosonic DM to standard model particles. Instead, in order to interpret laboratory measurements (even in the event of a discovery), it is necessary to account for the stochastic nature of such a virialized ultralight field (VULF). The constraints inferred from several previous null experiments searching for ultralight bosonic DM were overestimated by factors ranging from 3 to 10 depending on experimental details, model assumptions, and choice of inference framework.

astro-ph.CO↗

Rapid online solid-state battery diagnostics with optically pumped magnetometers

Solid state battery technology is motivated by the desire to deliver flexible power storage in a safe and efficient manner. The increasingly widespread use of batteries from mass-production facilities highlights the need for a rapid and sensitive diagnostic for identifying battery defects. We demonstrate the use of atomic magnetometry to measure the magnetic fields around miniature solid-state battery cells. These fields encode information about battery manufacturing defects, state of charge, impurities, or can provide important insights into ageing processes. Compared with SQUID-based magnetometry, the availability of atomic magnetometers, however, highlights the possibility for a low-cost, portable, and flexible implementation of battery quality-control and characterization technology.

physics.app-ph↗

Molecular Parity Nonconservation in Nuclear Spin Couplings

The weak interaction does not conserve parity, which is apparent in many nuclear and atomic phenomena. However, thus far, parity nonconservation has not been observed in molecules. Here we consider nuclear-spin-dependent parity nonconserving contributions to the molecular Hamiltonian. These contributions give rise to a parity nonconserving indirect nuclear spin-spin coupling which can be distinguished from parity conserving interactions in molecules of appropriate symmetry, including diatomic molecules. We estimate the magnitude of the coupling, taking into account relativistic corrections. Finally, we propose and simulate an experiment to detect the parity nonconserving coupling using liquid- or gas-state zero-field nuclear magnetic resonance of electrically oriented molecules and show that $^{1}$H$^{19}$F should give signals within the detection limits of current atomic vapor-cell magnetometers.

physics.chem-ph↗

Two-Dimensional Single- and Multiple-Quantum Correlation Spectroscopy in Zero-Field Nuclear Magnetic Resonance

We present single- and multiple-quantum correlation $J$-spectroscopy detected in zero ($<\!\!1$~$μ$G) magnetic field using a \Rb vapor-cell magnetometer. At zero field the spectrum of ethanol appears as a mixture of \carbon isotopomers, and correlation spectroscopy is useful in separating the two composite spectra. We also identify and observe the zero-field equivalent of a double-quantum transition in ${}^{13}$C$_2$-acetic acid, and show that such transitions are of use in spectral assignment. Two-dimensional spectroscopy further improves the high resolution attained in zero-field NMR since selection rules on the coherence-transfer pathways allow for the separation of otherwise overlapping resonances into distinct cross-peaks.

physics.chem-ph↗

Zero- to Ultralow-Field Nuclear Magnetic Resonance $J$-Spectroscopy with Commercial Atomic Magnetometers

Zero- to ultralow-field nuclear magnetic resonance (ZULF NMR) is an alternative spectroscopic method to high-field NMR, in which samples are studied in the absence of a large magnetic field. Unfortunately, there is a large barrier to entry for many groups, because operating the optical magnetometers needed for signal detection requires some expertise in atomic physics and optics. Commercially available magnetometers offer a solution to this problem. Here we describe a simple ZULF NMR configuration employing commercial magnetometers, and demonstrate sufficient functionality to measure samples with nuclear spins prepolarized in a permanent magnet or initialized using parahydrogen. This opens the possibility for other groups to use ZULF NMR, which provides a means to study complex materials without magnetic susceptibility-induced line broadening, and to observe samples through conductive materials.

physics.chem-ph↗

Battery Diagnostics with Sensitive Magnetometry

The ever-increasing demand for high-capacity rechargeable batteries highlights the need for sensitive and accurate diagnostic technology for determining the state of a cell, for identifying and localizing defects, or for sensing capacity loss mechanisms. Here, we demonstrate the use of atomic magnetometry to map the weak induced magnetic fields around a Li-ion battery cell as a function of state of charge and upon introducing mechanical defects. These measurements provide maps of the magnetic susceptibility of the cell, which follow trends characteristic for the battery materials under study upon discharge. In addition, the measurements reveal hitherto unknown long time-scale transient internal current effects, which were particularly pronounced in the overdischarged regime. The diagnostic power of this technique is promising for the assessment of cells in research, quality control, or during operation, and could help uncover details of charge storage and failure processes in cells.

physics.app-ph↗

Constraints on bosonic dark matter from ultralow-field nuclear magnetic resonance

The nature of dark matter, the invisible substance making up over $80\%$ of the matter in the Universe, is one of the most fundamental mysteries of modern physics. Ultralight bosons such as axions, axion-like particles or dark photons could make up most of the dark matter. Couplings between such bosons and nuclear spins may enable their direct detection via nuclear magnetic resonance (NMR) spectroscopy: as nuclear spins move through the galactic dark-matter halo, they couple to dark-matter and behave as if they were in an oscillating magnetic field, generating a dark-matter-driven NMR signal. As part of the Cosmic Axion Spin Precession Experiment (CASPEr), an NMR-based dark-matter search, we use ultralow-field NMR to probe the axion-fermion "wind" coupling and dark-photon couplings to nuclear spins. No dark matter signal was detected above background, establishing new experimental bounds for dark-matter bosons with masses ranging from $1.8\times 10^{-16}$ to $7.8\times 10^{-14}$ eV.

hep-ex↗

Search for axionlike dark matter with a liquid-state nuclear spin comagnetometer

We report the results of a search for axionlike dark matter using nuclear magnetic resonance (NMR) techniques. This search is part of the multi-faceted Cosmic Axion Spin Precession Experiment (CASPEr) program. In order to distinguish axionlike dark matter from magnetic fields, we employ a comagnetometry scheme measuring ultralow-field NMR signals involving two different nuclei ($^{13}$C and $^{1}$H) in a liquid-state sample of acetonitrile-2-$^{13}$C ($^{13}$CH$_{3}$CN). No axionlike dark matter signal was detected above background. This result constrains the parameter space describing the coupling of the gradient of the axionlike dark matter field to nucleons to be $g_{aNN}<6\times 10^{-5}$ GeV$^{-1}$ (95$\%$ confidence level) for particle masses ranging from $10^{-22}$ eV to $1.3\times10^{-17}$ eV, improving over previous laboratory limits for masses below $10^{-21}$ eV. The result also constrains the coupling of nuclear spins to the gradient of the square of the axionlike dark matter field, improving over astrophysical limits by orders of magnitude over the entire range of particle masses probed.

hep-ex↗

Magnetic Gradiometer for Detection of Zero- and Ultralow-Field Nuclear Magnetic Resonance

Magnetic sensors are important for detecting nuclear magnetization signals in nuclear magnetic resonance (NMR). As a complementary analysis tool to conventional high-field NMR, zero- and ultralow-field (ZULF) NMR detects nuclear magnetization signals in the sub-microtesla regime. Current ZULF NMR systems are always equipped with high-quality magnetic shieldings to ensure that ambient magnetic field noise does not dwarf the magnetization signal. An alternative approach is to separate the magnetization signal from the noise based on their differing spatial profiles, as can be achieved using a magnetic gradiometer. Here, we present a gradiometric ZULF NMR spectrometer with a magnetic gradient noise of 17 fT_{rms}{cm}^{-1}{Hz}^{-1/2} in the frequency range of 100-400 Hz, based on a single vapor cell (0.7x0.7x1.0{cm}^3). With applied white magnetic-field noise, we show that the gradiometric spectrometer achieves 13-fold enhancement in the signal-to-noise ratio (SNR) compared to the single-channel configuration. By reducing the influence of common-mode magnetic noise, this work enables the use of compact and low-cost magnetic shields. Gradiometric detection may also prove to be beneficial for eliminating systematic errors in ZULF-NMR experiments searching for exotic spin-dependent interactions and molecular parity violation.

physics.atom-ph↗

Nuclear-spin comagnetometer based on a liquid of identical molecules

Atomic comagnetometers are used in searches for anomalous spin-dependent interactions. Magnetic field gradients are one of the major sources of systematic errors in such experiments. Here we describe a comagnetometer based on the nuclear spins within an ensemble of identical molecules. The dependence of the measured spin-precession frequency ratio on the first-order magnetic field gradient is suppressed by over an order of magnitude compared to a comagnetometer based on overlapping ensembles of different molecules. Our single-species comagnetometer is shown to be capable of measuring the hypothetical spin-dependent gravitational energy of nuclei at the $10^{-17}$ eV level, comparable to the most stringent existing constraints. Combined with techniques for enhancing the signal such as parahydrogen-induced polarization, this method of comagnetometry offers the potential to improve constraints on spin-gravity coupling of nucleons by several orders of magnitude.

physics.atom-ph↗

Nondestructive in-line sub-picomolar detection of magnetic nanoparticles in flowing complex fluids

Over the last decades, the use of magnetic nanoparticles in research and commercial applications has increased dramatically. However, direct detection of trace quantities remains a challenge in terms of equipment cost, operating conditions and data acquisition times, especially in flowing conditions within complex media. Here we present the in-line, non-destructive detection of magnetic nanoparticles using high performance atomic magnetometers at ambient conditions in flowing media. We achieve sub-picomolar sensitivities measuring $\sim$30 nm ferromagnetic iron and cobalt nanoparticles that are suitable for biomedical and industrial applications, under flowing conditions in water and whole blood. Additionally, we demonstrate real-time surveillance of the magnetic separation of nanoparticles from water and whole blood. Overall our system has the merit of inline direct measurement of trace quantities of ferromagnetic nanoparticles with so far unreached sensitivities and could be applied in the biomedical field (diagnostics and therapeutics) but also in the industrial sector.

physics.app-ph↗

The Cosmic Axion Spin Precession Experiment (CASPEr): a dark-matter search with nuclear magnetic resonance

The Cosmic Axion Spin Precession Experiment (CASPEr) is a nuclear magnetic resonance experiment (NMR) seeking to detect axion and axion-like particles which could make up the dark matter present in the universe. We review the predicted couplings of axions and axion-like particles with baryonic matter that enable their detection via NMR. We then describe two measurement schemes being implemented in CASPEr. The first method, presented in the original CASPEr proposal, consists of a resonant search via continuous-wave NMR spectroscopy. This method offers the highest sensitivity for frequencies ranging from a few Hz to hundreds of MHz, corresponding to masses $ m_{\rm a} \sim 10^{-14}$--$10^{-6}$ eV. Sub-Hz frequencies are typically difficult to probe with NMR due to the diminishing sensitivity of magnetometers in this region. To circumvent this limitation, we suggest new detection and data processing modalities. We describe a non-resonant frequency-modulation detection scheme, enabling searches from mHz to Hz frequencies ($m_{\rm a} \sim 10^{-17}$--$10^{-14} $ eV), extending the detection bandwidth by three decades.

physics.ins-det↗

Application of Spin-Exchange Relaxation-Free Magnetometry to the Cosmic Axion Spin Precession Experiment

The Cosmic Axion Spin Precession Experiment (CASPEr) seeks to measure oscillating torques on nuclear spins caused by axion or axion-like-particle (ALP) dark matter via nuclear magnetic resonance (NMR) techniques. A sample spin-polarized along a leading magnetic field experiences a resonance when the Larmor frequency matches the axion/ALP Compton frequency, generating precessing transverse nuclear magnetization. Here we demonstrate a Spin-Exchange Relaxation-Free (SERF) magnetometer with sensitivity $\approx 1~{\rm fT/\sqrt{Hz}}$ and an effective sensing volume of 0.1 $\rm{cm^3}$ that may be useful for NMR detection in CASPEr. A potential drawback of SERF-magnetometer-based NMR detection is the SERF's limited dynamic range. Use of a magnetic flux transformer to suppress the leading magnetic field is considered as a potential method to expand the SERF's dynamic range in order to probe higher axion/ALP Compton frequencies.

physics.atom-ph↗