arXiv subjects

Ilai Schwartz

Publications and source records attributed to Ilai Schwartz.

At least 19 recordsLinked to original sources

arXiv2026

Hierarchical Maximum Likelihood Estimation for Time-Resolved NMR Data

Metabolic monitoring and reaction rate estimation using hyperpolarized NMR technology requires accurate quantitative analysis of multidimensional data scenarios. Currently, this analysis is often performed in a two-stage procedure, which is prone to errors in uncertainty propagation and estimation. We propose an approach derived from a Bayesian hierarchical model that intrinsically propagates uncertainties and operates on the full data to maximize the precision at minimal uncertainty. In an analytic treatment, we reduce the estimation procedure to a least-squares optimization problem which can be understood as an extension of the Variable Projection (VarPro) approach for data scenarios with two predictors. We investigate the method's efficacy in two experiments with hyperpolarized metabolites recorded with conventional high-field NMR devices and a micronscale NMR setup using Nitrogen-Vacancy centers in diamond for detection, respectively. In both examples, the new approach improves estimates compared to Fourier methods and proves operational advantages over a two-stage procedure employing VarPro. While the approach presented is motivated by NMR analysis, it is straightforwardly applicable to further estimation scenarios with similar data structure, such as time-resolved photospectroscopy.

q-bio.QM↗

arXiv2026

Robust nuclear hyperpolarization of small molecules through intermolecular transfer of parahydrogen-derived polarization

The recent advent of hyperpolarization techniques, which can enhance NMR signals by several orders of magnitude relative to thermally polarized samples, has enabled applications traditionally out of reach due to the inherently low sensitivity of NMR techniques. However, a high barrier to entry remains, as most hyperpolarization approaches either require complex instrumentation or are applicable only to a relatively small set of molecules. Here we introduce PHIPNOE, a platform that directly addresses both limitations. PHIPNOE is based on parahydrogen-induced polarization (PHIP), which is well-established as a scalable route to hyperpolarization requiring minimal instrumentation, but has been mostly restricted to molecules that undergo specific chemical reactions. We overcome this barrier by tailoring PHIP to create highly polarized, highly concentrated solutions of one specific molecule, which acts as an intermediate source of polarization. This 'source molecule' then distributes polarization to a broad range of target molecules mixed into the solution, via the spin polarization-induced nuclear Overhauser effect (SPINOE). We investigate chemical influences on PHIPNOE, and develop a predictive model to estimate enhancement based on molecular mass and T1 relaxation times. A complete run from PHIP hyperpolarization to PHIPNOE polarization transfer and signal detection takes less than one minute, the approach does not require any modifications to the NMR spectrometer, and enhancements are repeatable across molecular classes. PHIPNOE thus enables applications including single-shot multidimensional NMR, real-time monitoring of dynamic processes, and, with 300-fold signal amplification demonstrated on a benchtop spectrometer, practical low-field NMR, where we show enhanced sensitivity in detecting per- and polyfluoroalkyl substances (PFAS).

physics.chem-ph↗

arXiv2026

PIQC: Scalable Distributed Quantum Computing via Photonic Integration of Designed Molecular Quantum Nodes

There is a growing consensus that large-scale, fault-tolerant quantum computing (FTQC) necessitates high-fidelity photonic interconnects to overcome the scaling limits of monolithic architectures. However, most current platforms were not originally designed for native photonic connectivity and require significant engineering overhead. To overcome these fundamental hardware limitations, we recently introduced a rationally designed organic molecule that serves as an ideal quantum node, featuring a robust qubit-photon interface (QPI) and a long-lived nuclear-spin register. In this work, we present PIQC (Photonic Integrated Quantum Circuits), a distributed architecture designed to scale these molecular nodes into a functional quantum computer. The PIQC framework integrates five mutually reinforcing innovations: (i) Designer molecular qubits, i.e. carbene molecules in an isosteric host that provide millisecond-coherence electron spins with high spectral stability and spin-dependent optical emission, (ii) deterministic nuclear registers made of synthetically placed $^{13}$C or $^{14}$N labels that enable fast ($\sim 1~μ$s), high-fidelity electron-nuclear gates, (iii) hybrid photonic integration, which allows molecular films to seamlessly integrate with existing mature fabrication technologies, e.g. thin-film lithium niobate (TFLN), (iv) heralded entanglement protocols that can tolerate up to 70% photon loss, and (v) stairway Floquetification, i.e. high-rate quantum low-density parity-check (qLDPC) codes that are converted into Floquet codes, reducing syndrome extraction to weight-two Bell-pair measurements that match PIQC's networked hardware. PIQC offers a hardware-efficient, commercially viable pathway toward a utility-scale quantum computer based on distributed FTQC.

quant-ph↗

arXiv2026

A Single-Molecule Spin-Photon Interface

Optical interfaces that connect long-lived spin qubits to photons are a central requirement for quantum networking and distributed quantum information processing. Currently, solid-state atomic defects are leading candidates due to their inherent spin and optical coherence. Building on these advancements, synthetically tailored molecular systems represent a fundamental change in the field, utilizing precise atomic control and consistent bottom-up assembly. However, the lack of a robust spin-photon interface combining bright fluorescence, high spectral stability, and the persistent spin lifetimes inherent to ground-state systems has prohibited the detection of individual molecular qubits. Here we show that a triplet ground state carbene molecule, embedded within a structurally matched host crystal, functions as a robust spin-photon interface with single-molecule addressability. The system exhibits narrow zero-phonon lines, spectral stability over more than an hour, spin-selective optical transitions and single-molecule optically detected magnetic resonance. Coherent control yields millisecond-scale dynamical-decoupling coherence and tens-of-milliseconds spin relaxation at a temperature of 4.5 K. These results establish molecular qubits as a viable platform for single-emitter quantum optics while preserving the advantages of bottom-up chemical design and processable materials.

quant-ph↗

arXiv2026

Improved SABRE hyperpolarisation using pulse sequences to reduce effective coupling

Hyperpolarisation using Signal Amplification By Reversible Exchange (SABRE) is a convenient method for high repeatability studies. The core of this technique is polarisation transfer to the target substrate during an on-going chemical exchange process. Typically, polarisation transfer is achieved as fast as possible. In this study we employ NMR sequences that on contrary slow down the polarisation transfer and yet demonstrate improved performance. Simulations confirm that such methods can lead to high polarisation yield in SABRE system that exhibit higher magnetic inequivalence and lower chemical exchange rate.

physics.chem-ph↗

arXiv2025

Quantum Memory Enhanced Multipoint Correlation Spectroscopy for Statistically Polarized NMR

Nuclear magnetic resonance spectroscopy with solid-state spin sensors is a promising pathway for the detection of nuclear spins at the micro- and nanoscale. Although many nanoscale experiments rely on a single sensor spin for the detection of the signal, leveraging spin ensembles can enhance sensitivity, particularly in cases in which the signal merely originates from statistically polarized nuclear spins. In this work, we introduce multipoint correlation spectroscopy, that combines the advantages of two well-established methods -- correlation spectroscopy and quantum heterodyne detection -- to enable temporally efficient measurements of statistically polarized samples at the nanoscale with spin ensembles. We present a theoretical framework for this approach and demonstrate an experimental proof of concept with a nitrogen vacancy center in diamond. We achieve single hertz uncertainty in the estimated signal frequency, highlighting the potential applications of the technique for nanoscale nuclear magnetic resonance.

quant-ph↗

arXiv2025

PHIP Sequences and Dipolar Fields

Para-hydrogen induced polarization (PHIP) achieves efficient hyperpolarisation of nuclear spins with the transfer of the singlet order of parahydrogen to target molecules through catalytic hydrogenation reactions and subsequent coherent control of the spin dynamics. However, in realistic conditions B0/B1 inhomogeneities lead to significant reduction in the polarization transfer efficiency. Moreover, in high-concentration samples, dipolar fields arising from the magnetisation of the sample can degrade polarisation transfer efficiency significantly. In this work, we present a theoretical framework and a comprehensive analysis of both pulsed and continuous-wave (CW) control sequences designed to mitigate the detrimental effects of dipolar fields, $B_0/B_1$ inhomogeneities, and moderate chemical shifts. By combining tools from average Hamiltonian theory with detailed numerical simulations, we introduce and characterise a wide range of transfer sequences, including dipolar-field adjusted and dipolar-field suppressing protocols. We identify conditions under which dipolar interactions either hinder or, perhaps surprisingly, stabilise polarization transfer, depending on the sequence structure. Our results offer practical guidance for the selection and design of PHIP transfer sequences under realistic experimental constraints and open pathways toward robust hyperpolarisation in concentrated liquid-state NMR samples.

quant-ph↗

arXiv2024

Robust Parahydrogen-Induced Polarization at High Concentrations

Parahydrogen-Induced Polarization (PHIP) is a potent technique for generating target molecules with high nuclear spin polarization. The PHIP process involves a chemical reaction between parahydrogen and a target molecule, followed by the transformation of nuclear singlet spin order into magnetization of a designated nucleus through magnetic field manipulations. Although the singlet-to-magnetization polarization transfer process works effectively at moderate concentrations, it is observed to become much less efficient at high molar polarization, defined as the product of polarization and concentration. This strong dependence on the molar polarization is attributed to interference from the field produced by the sample's magnetization during polarization transfer, which leads to complex dynamics and can severely impact the scalability of the technique. We address this challenge with a pulse sequence that negates the influence of the distant dipolar field, while simultaneously achieving singlet-to-magnetization polarization transfer to the desired target spins, free from restrictions on the molar polarization.

physics.chem-ph↗

arXiv2023

Towards a unified picture of polarization transfer -- pulsed DNP and chemically equivalent PHIP

Nuclear spin hyperpolarization techniques, such as dynamic nuclear polarization (DNP) and parahydrogen-induced polarization (PHIP), have revolutionized nuclear magnetic resonance and magnetic resonance imaging. In these methods, a readily available source of high spin order, either electron spins in DNP or singlet states in hydrogen for PHIP, is brought into close proximity with nuclear spin targets, enabling efficient transfer of spin order under external quantum control. Despite vast disparities in energy scales and interaction mechanisms between electron spins in DNP and nuclear singlet states in PHIP, a pseudo-spin formalism allows us to establish an intriguing equivalence. As a result, the important low-field polarization transfer regime of PHIP can be mapped onto an analogous system equivalent to pulsed-DNP. This establishes a correspondence between key polarization transfer sequences in PHIP and DNP, facilitating the transfer of sequence development concepts. This promises fresh insights and significant cross-pollination between DNP and PHIP polarization sequence developers.

quant-ph↗

arXiv2022

Power-law scaling of correlations in statistically polarised nano-NMR

Diffusion noise is a major source of spectral line broadening in liquid state nano-scale nuclear magnetic resonance with shallow nitrogen-vacancy centres, whose main consequence is a limited spectral resolution. This limitation arises by virtue of the widely accepted assumption that nuclear spin signal correlations decay exponentially in nano-NMR. However, a more accurate analysis of diffusion shows that correlations survive for a longer time due to a power-law scaling, yielding the possibility for improved resolution and altering our understanding of diffusion at the nano-scale. Nevertheless, such behaviour remains to be demonstrated in experiments. Using three different experimental setups and disparate measurement techniques, we present overwhelming evidence of power-law decay of correlations. These result in sharp-peaked spectral lines, for which diffusion broadening need not be a limitation to resolution.

quant-ph↗

arXiv2022

Radio-Frequency Sweeps at μT Fields for Parahydrogen-Induced Polarization of Biomolecules

Magnetic resonance imaging of $^{13}$C-labeled metabolites enhanced by parahydrogen-induced polarization (PHIP) can enable real-time monitoring of processes within the body. We introduce a robust, easily implementable technique for transferring parahydrogen-derived singlet order into 13C magnetization using adiabatic radio-frequency sweeps at $μ$T fields. We experimentally demonstrate the applicability of this technique to several molecules, including some molecules relevant for metabolic imaging, where we show significant improvements in the achievable polarization, in some cases reaching above 60%. Furthermore, we introduce a site-selective deuteration scheme, where deuterium is included in the coupling network of a pyruvate ester to enhance the efficiency of the polarization transfer. These improvements are enabled by the fact that the transfer protocol avoids relaxation induced by strongly coupled quadrupolar nuclei.

physics.chem-ph↗

arXiv2022

Macroscopic Hyperpolarization Enhanced with Quantum Optimal Control

Hyperpolarization of nuclear spins enhances nuclear magnetic resonance signals, which play a key role for imaging and spectroscopy in the natural and life sciences. This signal amplification unlocks previously inaccessible techniques, such as metabolic imaging of cancer cells. In this work, electron spins from the photoexcited triplet state of pentacene-doped naphthalene crystals are used to polarize surrounding protons. As existing strategies are rendered less effective by experimental constraints, they are replaced with optimal control pulses designed with RedCRAB. In contrast to previous optimal control approaches, which consider an average single nucleus, this closed-loop optimization is macroscopic. A 28% improvement in signal and 15% faster polarization rate is observed. Additionally, a strategy called Autonomously-optimized Repeated Linear Sweep (ARISE) is introduced to efficiently tailor existing hyperpolarization sequences in the presence of experimental uncertainty to enhance their performance. ARISE is expected to be broadly applicable in many experimental settings.

quant-ph↗

arXiv2021

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↗

arXiv2020

Efficient Conversion of Nitrogen to Nitrogen-Vacancy Centers in Diamond Particles with High-Temperature Electron Irradiation

Fluorescent nanodiamonds containing negatively-charged nitrogen-vacancy (NV$^-$) centers are promising for a wide range of applications, such as for sensing, as fluorescence biomarkers, or to hyperpolarize nuclear spins. NV$^-$ centers are formed from substitutional nitrogen (P1 centers) defects and vacancies in the diamond lattice. Maximizing the concentration of NVs is most beneficial, which justifies the search for methods with a high yield of conversion from P1 to NV$^-$. We report here the characterization of surface cleaned fluorescent micro- and nanodiamonds, obtained by irradiation of commercial diamond powder with high-energy (10 MeV) electrons and simultaneous annealing at 800°C. Using this technique and increasing the irradiation dose, we demonstrate the creation of NV$^-$ with up to 25 % conversion yield. Finally, we monitor the creation of irradiation-induced spin-1 defects in microdiamond particles, which we associate with W16 and W33 centers, and investigate the effects of irradiation dose and particle size on the coherence time of NV$^-$.

cond-mat.mtrl-sci↗

arXiv2020

Limited-control metrology approaching the Heisenberg limit without entanglement preparation

Current metrological bounds typically assume full control over all particles that are involved in the protocol. Relaxing this assumption we study metrological performance when only limited control is available. As an example, we measure a static magnetic field when a fully controlled quantum sensor is supplemented by particles over which only global control is possible. We show that even for a noisy quantum sensor, a protocol that maps the magnetic field to a precession frequency can achieve transient super-Heisenberg scaling in measurement time and Heisenberg scaling in the particle number. This leads to an estimation uncertainty that approaches that achievable under full control to within a factor independent of the particle number for a given total time. Applications to hybrid sensing devices and the crucial role of the quantum character of the sensor are discussed.

quant-ph↗

arXiv2020

On the robustness of the NV-NMR spectrometer setup to magnetic field inhomogeneities

The NV-NMR spectrometer is a promising candidate for detection of NMR signals at the nano scale. Field inhomogeneities, however, are a major source of noise that limits spectral resolution in state of the art NV - NMR experiments and constitutes a major bottleneck in the development of nano scale NMR. Here we propose, a route in which this limitation could be circumvented in NV-NMR spectrometer experiments, by utilising the nanometric scale and the quantumness of the detector.

quant-ph↗

arXiv2019

Quantum control and sensing of nuclear spins by electron spins under power limitations

State of the art quantum sensing experiments targeting frequency measurements or frequency addressing of nuclear spins require to drive the probe system at the targeted frequency. In addition, there is a substantial advantage to perform these experiments in the regime of high magnetic fields, in which the Larmor frequency of the measured spins is large. In this scenario we are confronted with a natural challenge of controlling a target system with a very high frequency when the probe system cannot be set to resonance with the target frequency. In this contribution we present a set of protocols that are capable of confronting this challenge, even at large frequency mismatches between the probe system and the target system, both for polarisation and for quantum sensing.

quant-ph↗

arXiv2018

Pulsed polarisation for robust DNP

Dynamical nuclear polarisation (DNP) is an important technique that uses polarisation transfer from electron to nuclear spins to achieve nuclear hyperpolarisation. As the electron spin of the nitrogen vacancy (NV) centres in diamond can be optically initialised nearly perfectly even at room temperature and ambient conditions, new opportunities become possible by the combination of efficient DNP with optically polarised NV centres. Among such applications are nanoscale nuclear magnetic resonance spectroscopy of liquids, hyperpolarised nanodiamonds as MRI contrast agents as well as the initialisation of nuclear spin based diamond quantum simulators. Current realisations of DNP perform the polarisation transfer by achieving energetic resonance between electrons and nuclei via carefully tuned microwave fields or by using quasi-adiabatic sweep-based schemes across resonance points. The former limits robustness against control errors while the latter limits polarisation rates, making the realisation of the applications extremely challenging. Here we introduce the concept of Hamiltonian engineering by pulse sequences and use it for the systematic design of polarisation sequences that are simultaneously robust and fast. We derive sequences theoretically and demonstrate experimentally that they are capable of efficient polarisation transfer from an optically polarised nitrogen-vacancy centre in diamond to the surrounding $^{13}$C nuclear spin bath even in the presence of control errors, making it an ideal tool for the realisation of the above NV centre based applications.

quant-ph↗