arXiv subjects

Alexander Pines

Publications and source records attributed to Alexander Pines.

At least 19 recordsLinked to original sources

arXiv2020

Zero-Field J-spectroscopy of Quadrupolar Nuclei

Zero- to ultralow-field nuclear magnetic resonance (ZULF NMR) is a powerful version of NMR that allows studying molecules and their transformations in the regime dominated by intrinsic spin-spin interactions. While spin dynamics at zero magnetic field can be probed indirectly - via shuttling a sample that underwent evolution at zero field to a high-field NMR spectrometer for detection - J-spectra can also be measured directly at zero field by using non-inductive sensors, for example, atomic magnetometers. To date, no zero-field J-spectra of molecules featuring the coupling to quadrupolar nuclei were reported. Here we show that zero-field J-spectra can be collected from molecules containing quadrupolar nuclei with I = 1 and demonstrate this for solutions containing various isotopologues of ammonium cations, namely, 14NH4+ and 15NDxH(4-x)+ (where x = 0, 1, 2, or 3). Lower ZULF NMR signals are observed for molecules containing larger numbers of deuterons compared to protons; this is attributed to less overall magnetization and not to the scalar relaxation of the second kind. Values for the 15N-1H and 14N-1H J-couplings of -73.416(3) Hz, 52.395(2) Hz, respectively, are extracted from the ZULF NMR spectra. Precision measurement of the J(15NH)/J(14NH) ratio resulted in the value within a range of 1.4009-1.4013; this is statistically different from {\gamma_{15N}}/{\gamma_{14N}}=1.4027 reported in the literature indicating the presence of the primary isotope effect. We analyze the energy structure for the studied molecular cations in detail and demonstrate that spectral line positions depend dramatically both on the sign of each J-coupling and on the magnetic pulse length.

physics.chem-ph↗

arXiv2020

Magnetic-field-induced delocalization in hybrid electron-nuclear spin ensembles

We use field-cycling-assisted dynamic nuclear polarization and continuous radio-frequency (RF) driving over a broad spectral range to demonstrate magnetic-field-dependent activation of nuclear spin transport from strongly-hyperfine-coupled 13C sites in diamond. We interpret our observations with the help of a theoretical framework where nuclear spin interactions are mediated by electron spins. In particular, we build on the results from a 4-spin toy model to show how otherwise localized nuclear spins must thermalize as they are brought in contact with a larger ancilla spin network. Further, by probing the system response to a variable driving field amplitude, we witness stark changes in the RF-absorption spectrum, which we interpret as partly due to contributions from heterogeneous multi-spin sets, whose 'zero-quantum' transitions become RF active thanks to the hybrid electron-nuclear nature of the system. These findings could prove relevant in applications to dynamic nuclear polarization, spin-based quantum information processing, and nanoscale sensing.

cond-mat.mes-hall↗

arXiv2020

Optically pumped spin polarization as a probe of many-body thermalization

The interplay between disorder and transport is a problem central to the understanding of a broad range of physical processes, most notably the ability of a system to reach thermal equilibrium. Disorder and many body interactions are known to compete, with the dominance of one or the other giving rise to fundamentally different dynamical phases. Here we investigate the spin diffusion dynamics of 13C in diamond, which we dynamically polarize at room temperature via optical spin pumping of engineered color centers. We focus on low-abundance, strongly hyperfine-coupled nuclei, whose role in the polarization transport we expose through the integrated impact of variable radio-frequency excitation on the observable bulk 13C magnetic resonance signal. Unexpectedly, we find good thermal contact throughout the nuclear spin bath, virtually independent of the hyperfine coupling strength, which we attribute to effective carbon-carbon interactions mediated by the electronic spin ensemble. In particular, observations across the full range of hyperfine couplings indicate the nuclear spin diffusion constant takes values up to two orders of magnitude greater than that expected from homo-nuclear spin couplings. Our results open intriguing opportunities to study the onset of thermalization in a system by controlling the internal interactions within the bath.

quant-ph↗

arXiv2020

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 ($<\!\!1$~$\mu$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↗

arXiv2019

Erwin L. Hahn: A Biographical Memoir

Erwin Louis Hahn was one of the most innovative and influential physical scientists in recent history, impacting generations of scientists through his work in nuclear magnetic resonance (NMR), optics, and the intersection of these two fields. Starting with his discovery of the spin echo, a phenomenon of monumental significance and practical importance, Hahn launched a major revolution in how we think about spin physics, with numerous implications to follow in many other areas of science. Students of NMR and coherent optics quickly discover that many of the key concepts and techniques in these fields derive directly from his work.

physics.hist-ph↗

arXiv2019

Two-electron-spin ratchets as a platform for microwave-free dynamic nuclear polarization of arbitrary material targets

Optically-pumped color centers in semiconductor powders can potentially induce high levels of nuclear spin polarization in surrounding solids or fluids at or near ambient conditions, but complications stemming from the random orientation of the particles and the presence of unpolarized paramagnetic defects hinder the flow of polarization beyond the defect's host material. Here, we theoretically study the spin dynamics of interacting nitrogen-vacancy (NV) and substitutional nitrogen (P1) centers in diamond to show that outside protons spin-polarize efficiently upon a magnetic field sweep across the NV-P1 level anti-crossing. The process can be interpreted in terms of an NV-P1 spin ratchet, whose handedness - and hence the sign of the resulting nuclear polarization - depends on the relative timing of the optical excitation pulse. Further, we find that the polarization transfer mechanism is robust to NV misalignment relative to the external magnetic field, and efficient over a broad range of electron-electron and electron-nuclear spin couplings, even if proxy spins feature short coherence or spin-lattice relaxation times. Therefore, these results pave the route towards the dynamic nuclear polarization of arbitrary spin targets brought in proximity with a diamond powder under ambient conditions.

quant-ph↗

arXiv2019

Dynamics of frequency-swept nuclear spin optical pumping in powdered diamond at low magnetic fields

A broad effort is underway to improve the sensitivity of nuclear magnetic resonance through the use of dynamic nuclear polarization. Nitrogen-vacancy (NV) centers in diamond offer an appealing platform because these paramagnetic defects can be optically polarized efficiently at room temperature. However, work thus far has been mainly limited to single crystals because most polarization transfer protocols are sensitive to misalignment between the NV and magnetic field axes. Here we study the spin dynamics of NV-13C pairs in the simultaneous presence of optical excitation and microwave frequency sweeps at low magnetic fields. We show that a subtle interplay between illumination intensity, frequency sweep rate, and hyperfine coupling strength leads to efficient, sweep-direction-dependent 13C spin polarization over a broad range of orientations of the magnetic field. In particular, our results strongly suggest that finely-tuned, moderately coupled nuclear spins are key to the hyperpolarization process, which makes this mechanism distinct from other known dynamic polarization channels. These findings pave the route to applications where powders are intrinsically advantageous, including the hyper-polarization of target fluids in contact with the diamond surface or the use of hyperpolarized particles as contrast agents for in-vivo imaging.

cond-mat.mes-hall↗

arXiv2019

Hyperpolarized relaxometry based nuclear T1 noise spectroscopy in hybrid diamond quantum registers

Understanding the origins of spin lifetimes in hybrid quantum systems is a matter of current importance in several areas of quantum information and sensing. Methods that spectrally map spin relaxation processes provide insight into their origin and can motivate methods to mitigate them. In this paper, using a combination of hyperpolarization and precision field cycling over a wide range (1mT-7T), we map frequency dependent relaxation in a prototypical hybrid system of 13C nuclear spins in diamond coupled to Nitrogen Vacancy centers. Nuclear hyperpolarization through the optically pumped NV electrons allows signal time savings for the measurements exceeding million-fold over conventional methods. We observe that 13C lifetimes show a dramatic field dependence, growing rapidly with field up to 100mT and saturating thereafter. Through a systematic study with increasing substitutional electron (P1 center) concentration as well as 13C enrichment levels, we identify the operational relaxation channels for the nuclei in different field regimes. In particular, we demonstrate the dominant role played by the 13C nuclei coupling to the interacting P1 electronic spin bath. These results pave the way for quantum control techniques for dissipation engineering to boost spin lifetimes in diamond, with applications ranging from engineered quantum memories to hyperpolarized 13C imaging.

quant-ph↗

arXiv2018

Room temperature "Optical Nanodiamond Hyperpolarizer": physics, design and operation

Dynamic Nuclear Polarization (DNP) is a powerful suite of techniques that deliver multifold signal enhancements in NMR and MRI. The generated athermal spin states can also be exploited for quantum sensing and as probes for many-body physics. Typical DNP methods require use of cryogens, large magnetic fields, and high power microwaves, which are expensive and unwieldy. Nanodiamond particles, rich in Nitrogen-Vacancy (NV) centers, have attracted attention as alternative DNP agents because they can potentially be optically hyperpolarized at room temperature. Indeed the realization of a miniature "optical nanodiamond hyperpolarizer", where 13C nuclei are optically hyperpolarized has been a longstanding goal but has been technically challenging to achieve. Here, unravelling new physics underlying an optical DNP mechanism first introduced in [Ajoy et al., Sci. Adv. 4, eaar5492 (2018)], we report the realization of such a device in an ultracompact footprint and working fully at room temperature. Instrumental requirements are very modest: low polarizing fields, extremely low optical and microwave irradiation powers, and convenient frequency ranges that enable device miniaturization. We obtain best reported optical 13C hyperpolarization in diamond particles exceeding 720 times of the thermal 7T value (0.86% bulk polarization), corresponding to a ten-million-fold gain in NMR averaging time. In addition the hyperpolarization signal can be background-suppressed by over two-orders of magnitude and retained for multiple-minute long periods. Besides compelling applications in quantum sensing, and bright-contrast MRI imaging, this work paves the way for low-cost DNP platforms that relay the 13C polarization to liquids in contact with the high surface-area particles. This will ultimately allow development of miniature "quantum-assisted" NMR spectrometers for chemical analysis.

quant-ph↗

arXiv2017

Multi-spin-assisted optical pumping of bulk 13C nuclear spin polarization in diamond

One of the most remarkable properties of the nitrogen-vacancy (NV) center in diamond is that optical illumination initializes its electronic spin almost completely, a feature that can be exploited to polarize other spin species in their proximity. Here we use field-cycled nuclear magnetic resonance (NMR) to investigate the mechanisms of spin polarization transfer from NVs to 13C spins in diamond at room temperature. We focus on the dynamics near 51 mT, where a fortuitous combination of energy matching conditions between electron and nuclear spin levels gives rise to alternative polarization transfer channels. By monitoring the 13C spin polarization as a function of the applied magnetic field, we show 13C spin pumping takes place via a multi-spin cross relaxation process involving the NV- spin and the electronic and nuclear spins of neighboring P1 centers. Further, we find that this mechanism is insensitive to the crystal orientation relative to the magnetic field, although the absolute level of 13C polarization - reaching up to ~3% under optimal conditions - can vary substantially depending on the interplay between optical pumping efficiency, photo-generated carriers, and laser-induced heating.

quant-ph↗

arXiv2017

Optically-pumped dynamic nuclear hyperpolarization in $^{13}$C enriched diamond

We investigate nuclear spin hyperpolarization from nitrogen vacancy centers in isotopically enriched diamonds with $^{13}$C concentrations up to 100%. $^{13}$C enrichment leads to hyperfine structure of the nitrogen vacancy electron spin resonance spectrum and as a result the spectrum of dynamic nuclear polarization. We show that strongly-coupled $^{13}$C spins in the first shell surrounding a nitrogen vacancy center generate resolved hyperfine splittings, but do not act as an intermediary in the transfer of hyperpolarization of bulk nuclear spins. High levels of $^{13}$C enrichment are desirable to increase the efficiency of hyperpolarizaiton for magnetic resonance signal enhancement, imaging contrast agents, and as a platform for quantum sensing and many-body physics.

quant-ph↗

arXiv2017

Understanding the magnetic resonance spectrum of nitrogen vacancy centers in an ensemble of randomly-oriented nanodiamonds

Nanodiamonds containing nitrogen vacancy (NV-) centers show promise for a number of emerging applications including targeted in vivo imaging and generating nuclear spin hyperpolarization for enhanced NMR spectroscopy and imaging. Here, we develop a detailed understanding of the magnetic resonance behavior of NV- centers in an ensemble of nanodiamonds with random crystal orientations. Two-dimensional optically detected magnetic resonance spectroscopy reveals the distribution of energy levels, spin populations, and transition probabilities that give rise to a complex spectrum. We identify overtone transitions that are inherently insensitive to crystal orientation and give well-defined transition frequencies that access the entire nanodiamond ensemble. These transitions may be harnessed for high-resolution imaging and generation of nuclear spin hyperpolarization. The data are well described by numerical simulations from the zero- to high-field regimes, including the intermediate regime of maximum complexity. We evaluate the prospects of nanodiamond ensembles specifically for nuclear hyperpolarization and show that frequency-swept dynamic nuclear polarization may transfer a large amount of the NV- center's hyperpolarization to nuclear spins by sweeping over a small region of its spectrum.

quant-ph↗

arXiv2017

Measuring molecular parity nonconservation using nuclear magnetic resonance spectroscopy

The weak interaction does not conserve parity and therefore induces energy shifts in chiral enantiomers that should in principle be detectable in molecular spectra. Unfortunately, the magnitude of the expected shifts are small and in spectra of a mixture of enantiomers, the energy shifts are not resolvable. We propose a nuclear magnetic resonance (NMR) experiment in which we titrate the chirality (enantiomeric excess) of a solvent and measure the diasteriomeric splitting in the spectra of a chiral solute in order to search for an anomalous offset due to parity nonconservation (PNC). We present a proof-of-principle experiment in which we search for PNC in the \textsuperscript{13}C resonances of small molecules, and use the \textsuperscript{1}H resonances, which are insensitive to PNC, as an internal reference. We set a new constraint on molecular PNC in \textsuperscript{13}C chemical shifts at a level of $10^{-5}$\,ppm, and provide a discussion of important considerations in the search for molecular PNC using NMR spectroscopy.

physics.chem-ph↗

arXiv2017

Instrumentation for nuclear magnetic resonance in zero and ultralow magnetic field

We review instrumentation for nuclear magnetic resonance (NMR) in zero and ultra-low magnetic field (ZULF, below 0.1 $\mu$T) where detection is based on a low-cost, non-cryogenic, spin-exchange relaxation free (SERF) $^{87}$Rb atomic magnetometer. The typical sensitivity is 20-30 fT/Hz$^{1/2}$ for signal frequencies below 1 kHz and NMR linewidths range from Hz all the way down to tens of mHz. These features enable precision measurements of chemically informative nuclear spin-spin couplings as well as nuclear spin precession in ultra-low magnetic fields.

physics.ins-det↗

arXiv2015

Decoherence-protected transitions of nitrogen vacancy centers in 99% 13C-enriched diamond

Nitrogen vacancy (NV-) color centers in diamond are a prime candidate for use in quantum information devices, owing to their spin-1 ground state, straightforward optical initialization and readout, and long intrinsic coherence times in a room-temperature solid. While the 13C nuclear spin is often a dominant source of magnetic noise, we observe transitions between electron-nuclear hyperfine states of NV- centers in 99% 13C diamond that are robust to decoherence. At magnetic field strengths ranging from 550 - 900 G, these transitions are observable by optically detected magnetic resonance (ODMR), and exhibit linewidths narrowed by factors as high as ~130 at room temperature over typical electron-type transitions observed from this spin system. We anticipate the use of these decoherence-protected transitions, in combination with dynamical decoupling methods, for storage of quantum information.

quant-ph↗

arXiv2015

Measurement of Untruncated Nuclear Spin Interactions via Zero- to Ultra-Low-Field Nuclear Magnetic Resonance

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

physics.chem-ph↗

arXiv2015

Room-Temperature in situ Nuclear Spin Hyperpolarization from Optically-Pumped Nitrogen Vacancy Centers in Diamond

We report bulk, room-temperature hyperpolarization of 13C nuclear spins observed via high-field nuclear magnetic resonance (NMR). The hyperpolarization is achieved by optical pumping (OP) of nitrogen vacancy defect centers in diamond accompanied by dynamic nuclear polarization (DNP). The technique harnesses the large optically-induced spin polarization of NV- centers at room temperature, which is many orders of magnitude greater than thermal equilibrium polarization and typically achievable only at sub-Kelvin temperatures. Transfer of the spin polarization to the 13C nuclear spins is accomplished via a combination of OP and microwave irradiation. The OP/DNP is performed at 420 mT, where inductive detection of NMR is feasible, in contrast to the typically exploited level anticrossing regimes at 100 mT and 50 mT. Here, we report a bulk nuclear spin polarization of 6%. This polarization was generated in situ and detected with a standard, inductive NMR probe without the need for sample shuttling or precise crystal orientation. Hyperpolarization via OP/DNP should operate at arbitrary magnetic fields, enabling orders of magnitude sensitivity enhancement for NMR of solids and liquids at ambient conditions.

quant-ph↗

arXiv2014

Optically detected nuclear quadrupolar interaction of 14N in nitrogen-vacancy centers in diamond

We report sensitive detection of the nuclear quadrupolar interaction of the 14N nuclear spin of the nitrogen-vacancy (NV) center using the electron spin echo envelope modulation technique. We applied a weak transverse magnetic field to the spin system so that certain forbidden transitions became weakly allowed due to second-order effects involving the nonsecular terms of the hyperfine interaction. The weak transitions cause modulation of the electron spin-echo signal, and a theoretical analysis suggests that the modulation frequency is primarily determined by the nuclear quadrupolar frequency; numerical simulations confirm the analytical results and show excellent quantitative agreement with experiments. This is an experimentally simple method of detecting quadrupolar interactions, and it can be used to study spin systems with an energy structure similar to that of the nitrogen vacancy center.

quant-ph↗