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arXiv:2511.19244

Longitudinal Pulsed Dynamic Nuclear Polarization Transfer via Periodic Optimal Control

José P. Carvalho, Anders Bodholt Nielsen, David L. Goodwin, Nino Wili, Niels Chr. Nielsen

quant-phSubmitted Nov 24, 2025• Announced Nov 25, 2025
arXivHTMLPDF

Abstract

Taking inspiration from NMR spectroscopy, periodic irradiation schemes have recently shown remarkable performance when implemented into pulsed dynamic nuclear polarization (DNP) sequences. This has prompted considerable interest in development of broadband pulsed DNP sequences utilizing such schemes. On this background, most efforts have focused on solid-state NMR like transverse spin-locked pulse sequences whose performance in DNP applications may be compromised by the broadband capabilities of the initial excitation pulse. Leveraging the flexibility and robustness of optimal control theory combined with underlying insights from effective Hamiltonian theory, we present a new family of broadband DNP pulse sequences, termed LOOP (Longitudinally Optimized with Overarching Periodicity), that alleviates the excitation-pulse challenge by accomplishing longitudinal polarization transfer. These sequences define robust single-spin effective $z$ rotations, with impressive compensation towards microwave field inhomogeneity, and are capable of delivering DNP transfer with bandwidths exceeding 100 MHz, while employing a peak microwave field amplitude of only 32 MHz, at an external magnetic field of 0.35 T.

Comments
8 pages main text, 3 figures, 2 pages SI, 2 figures SI, 2 tables SI, TOC

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Taking inspiration from NMR spectroscopy, periodic irradiation schemes have recently shown remarkable performance when implemented into pulsed dynamic nuclear polarization (DNP) sequences. This has prompted considerable interest in development of broadband pulsed DNP sequences utilizing such schemes. On this background, most efforts have focused on solid-state NMR like transverse spin-locked pulse sequences whose performance in DNP applications may be compromised by the broadband capabilities of the initial excitation pulse. Leveraging the flexibility and robustness of optimal control theory combined with underlying insights from effective Hamiltonian theory, we present a new family of broadband DNP pulse sequences, termed LOOP (Longitudinally Optimized with Overarching Periodicity), that alleviates the excitation-pulse challenge by accomplishing longitudinal polarization transfer. These sequences define robust single-spin effective zzz rotations, with impressive compensation towards microwave field inhomogeneity, and are capable of delivering DNP transfer with bandwidths exceeding 100 MHz, while employing a peak microwave field amplitude of only 32 MHz, at an external magnetic field of 0.35 T.
Pulsed Dynamic Nuclear Polarization (DNP) is currently receiving substantial interest as a means to enhance the sensitivity of nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) by orders of magnitude. It has also received much attention as a central ingredient in many modalities of electron spin-involved quantum sensing. Relative to spin engineering associated with NMR, the design of efficient pulsed DNP experiments with a broad experimental scope are challenged by large electron-nuclear spin systems, large electron spin-involved interactions, and instrumental non-idealities and limitations. All of this may challenge traditional NMR-like theoretical and numerical pulse sequence engineering. Exploiting state-of-the-art instrumentation and taking advantage of the high sensitivity of DNP relative to NMR, we here demonstrate the use of combinations of Bayesian machine learning methods and constrained random walk procedures to design pulse sequences \textit{in situ}, by experiments, directly on the spin systems responding to spectrometer instructions. For trityl and nitroxide samples, it is demonstrated that efficient broadband DNP pulse sequences can be designed in situ with experimental protocols benchmarked against in silico analogs.
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In this paper, we study the design of pulse sequences for nuclear magnetic resonance spectroscopy as a problem of time optimal control of the unitary propagator. Radio-frequency pulses are used in coherent spectroscopy to implement a unitary transfer between states. Pulse sequences that accomplish a desired transfer should be as short as possible in order to minimize the effects of relaxation and to optimize the sensitivity of the experiments. Here, we give an analytical characterization of such time optimal pulse sequences applicable to coherence transfer experiments in multiple-spin systems. We have adopted a general mathematical formulation, and present many of our results in this setting, mindful of the fact that new structures in optimal pulse design are constantly arising. From a general control theory perspective, the problems we want to study have the following character. Suppose we are given a controllable right invariant system on a compact Lie group. What is the minimum time required to steer the system from some initial point to a specified final point? In nuclear magnetic resonance (NMR) spectroscopy and quantum computing, this translates to, what is the minimum time required to produce a unitary propagator? We also give an analytical characterization of maximum achievable transfer in a given time for the two-spin system.
PulsePol is an elegantly designed pulse-sequence-based quantum control scheme that enables polarization transfer between electron and nuclear spins, for example, in nitrogen-vacancy (NV) centers. However, previous analyses of PulsePol assumed very strong, near-ideal, instantaneous microwave pulses, which is rarely achievable at higher magnetic fields. We revisit the PulsePol scheme under finite-pulse constraints and show that its performance significantly degrades due to finite-pulse effects. Using bimodal Floquet theory, we identify the symmetry-breaking mechanism responsible for this deterioration in fidelity. By phase adjustment, we reestablish the proper symmetry of the interaction-frame spin Hamiltonian, leading to a sequence called Q-PulsePol, where "Q" reflects the restored quadrature symmetry. Our results demonstrate robustness to finite-pulse effects and improved polarization transfer efficiency, establishing Q-PulsePol as a practical and reliable scheme for bulk hyperpolarization of nuclear spins in solids using a single-mode (zero-quantum or double-quantum) transfer. This work bridges idealized quantum control with realistic pulse engineering, establishing design rules for spin-based quantum control protocols.
Experiments in coherent spectroscopy correspond to control of quantum-mechanical ensembles guiding them from initial to final target states. The control inputs (pulse sequences) that accomplish these transfers should be designed to minimize the effects of relaxation and to optimize the sensitivity of the experiments. For example in Nuclear Magnetic Resonance (NMR) spectroscopy, a question of fundamental importance is what is the maximum efficiency of polarization or coherence transfer between coupled spins in the presence of relaxation. Furthermore, what is the optimal pulse sequence which achieves this efficiency? This letter is a continuation of our previous work on the above problems. Here, we attempt to answer these questions for an Ising spin chain, under the presence of transverse relaxation. The methods presented in this paper are expected to find applications not only in coherent spectroscopy but also in quantum information processing.
PulsePol is an elegantly designed pulse-sequence-based quantum control scheme that enables polarization transfer between electron and nuclear spins. However, previous analyses of PulsePol assumed very strong, close to ideal, instantaneous microwave pulses, which is rarely achievable as one goes to higher magnetic fields. We revisit the PulsePol scheme under finite-pulse constraints and show that its performance significantly degrades because of finite-pulse effects. Using bimodal Floquet theory, we identify the symmetry-breaking mechanism responsible for this deteriorating fidelity. By phase adjustment, we reestablish the proper symmetry of the interaction-frame spin Hamiltonian—leading to a sequence called Q-PulsePol, where ‘Q’ reflects the restored quadrature symmetry. Our results demonstrate robustness to finite-pulse effects and improved polarization transfer efficiency, establishing Q-PulsePol as a practical and reliable scheme for bulk hyperpolarization of nuclear spins in solid-state using a single-mode (zero-quantum or double-quantum) transfer. This work bridges idealized quantum control with realistic pulse engineering, establishing design rules for spin-based quantum-control protocols.