arXiv subjects

Niels Chr. Nielsen

Publications and source records attributed to Niels Chr. Nielsen.

12 recordsLinked to original sources

arXiv2026

Solid-State NMR Dipolar Recoupling in Presence of Large Chemical Shielding Anisotropies by Quaternion-Based Effective Hamiltonian Optimal Control

Dipolar recoupling is a key element in magic-angle-spinning (MAS) solid-state NMR spectroscopy with reintroduced dipole-dipole coupling interactions providing information about internuclear distances and enabling transfer of polarization between spins in resolution-enhancing multiple-dimensional experiments. Such methods may be challenged in many important applications by the presence of large anisotropic nuclear spin interactions such as chemical shielding anisotropy. In this paper, we address this challenge by presenting quaternion-based optimal control. This is founded in single-spin operations enabling optimization of effective Hamiltonians with reduced influences from anisotropic shielding. Along with the principles underlying such optimizations, we present numerical and experimental demonstration of 19F to 13C polarization transfer in presence of 19F chemical shielding anisotropy.

physics.chem-ph↗

arXiv2026

Quadrature-Symmetric PulsePol for Robust Quantum Control Beyond the Ideal Pulse Approximation

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.

quant-ph↗

arXiv2026

In situ Learning-Based Spin Engineering of Pulsed Dynamic Nuclear Polarization

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.

physics.chem-ph↗

arXiv2026

Extending numerical simulations in SIMPSON: Electron paramagnetic resonance, dynamic nuclear polarisation, propagator splitting, pulse transients, and quadrupolar cross terms

Aimed at the simulation, design, and interpretation of advanced pulse experiments crossing the boundaries between nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR), including the rapidly emerging, hybrid discipline of pulsed dynamic nuclear polarisation (DNP), we present a host of novel features in the widely used SIMPSON software package addressing these aspects. Along with this come new features for advanced pulse sequence evaluation in terms of propagator splitting, high-order spin operator cross terms, and pulse phase transients. These fundamental new tools are introduced in a C++-based next generation of the SIMPSON software, which improves calculations speed in some aspects, is better prepared for further developments, and facilitates easier community contributions to the open-source software package.

physics.chem-ph↗

arXiv2025

Longitudinal Pulsed Dynamic Nuclear Polarization Transfer via Periodic Optimal Control

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.

quant-ph↗

arXiv2025

Controlling Effective Hamiltonians: Broadband Pulsed Dynamic Nuclear Polarization by Constrained Random Walk and Non-linear Optimization

We present constrained random walk (cRW) and figure of merit (FOM) based non-linear optimization procedures for systematic design and fundamental understanding of magnetic resonance experiments dressing bilinear and linear effective Hamiltonians to provide broadband polarization transfer. cRW can be used directly for fast random experiment design, or in combination with non-linear optimization or optimal control, leveraging the optimization of a FOM function for efficient control of linear and bilinear terms derived by exact effective Hamiltonian theory (EEHT). The efficacy of the combined cRW and FOM-based optimization approach is demonstrated by the design of broadband dynamic nuclear polarization (DNP) pulse sequences for static solids with an electron spin excitation bandwidth reaching 100 MHz.

physics.chem-ph↗

arXiv2025

Bridging DNP and MAS NMR dipolar recoupling -- from static single crystal to spinning powders

Spin engineering of advanced pulse sequences has had a transformative impact on the development of nuclear magnetic resonance (NMR) spectroscopy, to an extending degree also electron paramagnetic resonance (EPR), and the hybrid between the two, dynamic nuclear polarization (DNP). Based on a simple formalism, we demonstrate that (i) single-crystal static-sample optimisations may tremendously ease design of experiments for rotating powders and (ii) pulse sequences may readily be exchanged between these distinct spectroscopies. Specifically, we design broadband heteronuclear solid-state NMR magic-angle-spinning (MAS) dipolar recoupling experiments based on the recently developed PLATO (PoLarizAtion Transfer via non-linear Optimization) microwave (MW) pulse sequence optimized on a single crystal for powder static-sample DNP. Using this concept, we demonstrate design of ultra-broadband 13C-15N and 2H-13C cross-polarization experiments, using PLATO on the 13C radio-frequency (RF) channel and square/ramped or RESPIRATION (Rotor Echo Short Pulse IRrAdiaTION) RF irradiation on the 15N and 2H RF channels, respectively.

physics.chem-ph↗

arXiv2024

Observation of Dynamic Nuclear Polarization Echoes

It is demonstrated that the time evolution of the electron-nuclear polarization transfer process during pulsed dynamic nuclear polarization (DNP) can be reversed on a microsecond timescale, leading to the observation of DNP echoes. The DNP echoes are induced by consecutive application of two pulse trains that produce effective Hamiltonians that differ only in the sign of the effective hyperfine coupling. The experiments have been performed on a frozen solution of trityl radicals in water/glycerol on a home-built X-band EPR/DNP spectrometer at 80 K. We envisage that DNP echoes will play an important role in future development of pulsed DNP for sensitivity-enhanced NMR, hyperfine spectroscopy, and quantum sensing.

physics.chem-ph↗

arXiv2022

Designing broadband pulsed dynamic nuclear polarization sequences in static solids

Dynamic nuclear polarization (DNP) is an NMR hyperpolarization technique that mediates polarization transfer from highly polarized unpaired electrons to NMR-active nuclei via microwave (mw) irradiation. The ability to generate arbitrarily shaped mw pulses using arbitrary waveform generators opens up the opportunity to remarkably improve the robustness and versatility of DNP, in many ways resembling the early stages of pulsed NMR. We present here novel design principles based on single-spin vector effective Hamiltonian theory to develop new broadband DNP pulse sequences, namely an adiabatic XiX-DNP experiment and a broadband amplitude modulated signal enhanced (BASE) experiment. We demonstrate that the adiabatic BASE pulse sequence may achieve a DNP $^{1}$H enhancement factor of $\sim$ 360, a record that outperforms all previously known pulsed DNP sequences at $\sim$ 0.35 T and 80 K in static solids. The bandwidth of the BASE-DNP experiments is about 3 times the $^{1}$H Larmor frequency ($\sim$50 MHz).

physics.chem-ph↗

arXiv2018

Cryogen-Free dissolution Dynamic Nuclear Polarization polarizer operating at 3.35 T, 6.70 T and 10.1 T

Purpose: A novel dissolution dynamic nuclear polarization (dDNP) polarizer platform is presented. The polarizer meets a number of key requirements for in vitro, pre-clinical and clinical applications. Method: It uses no liquid cryogens, operates in continuous mode, accommodates a wide range of sample sizes up to and including those required for human studies, and is fully automated. Results: It offers a wide operational window both in terms of magnetic field, up to 10.1 T, and temperature, from room temperature down to 1.3 K. The polarizer delivers a 13C liquid state polarization for [1-13C]pyruvate of 70%. The build-up time constant in the solid state is approx. 1200 s (20 min), allowing a sample throughput of at least one sample per hour including sample loading and dissolution. Conclusion: We confirm the previously reported strong field dependence in the range 3.35 to 6.7 T, but see no further increase in polarization when increasing the magnetic field strength to 10.1 T for [1-13C]pyruvate and trityl. Using a custom dry magnet, cold head and recondensing, closed-cycle cooling system, combined with a modular DNP probe, automation and fluid handling systems; we have designed a unique dDNP system with unrivalled flexibility and performance.

physics.med-ph↗

arXiv2010

A smoothing monotonic convergent optimal control algorithm for NMR pulse sequence design

The past decade has demonstrated increasing interests in using optimal control based methods within coherent quantum controllable systems. The versatility of such methods has been demonstrated with particular elegance within nuclear magnetic resonance (NMR) where natural separation between coherent and dissipative spin dynamics processes has enabled coherent quantum control over long periods of time to shape the experiment to almost ideal adoption to the spin system and external manipulations. This has led to new design principles as well as powerful new experimental methods within magnetic resonance imaging, liquid-state and solid-state NMR spectroscopy. For this development to continue and expand, it is crucially important to constantly improve the underlying numerical algorithms to provide numerical solutions which are optimally compatible with implementation on current instrumentation and at same time are numerically stable and offer fast monotonic convergence towards the target. Addressing such aims, we here present a smoothing monotonically convergent algorithm for pulse sequence design in magnetic resonance which with improved optimization stability lead to smooth pulse sequence easier to implement experimentally and potentially understand within the analytical framework of modern NMR spectroscopy.

quant-ph↗

arXiv2007

Triple oscillating field technique for accurate measurements of couplings in homonuclear spin systems

We present a new concept for homonuclear dipolar recoupling in magic-angle-spinning (MAS) solid-state NMR experiments which avoids the problem of dipolar truncation. This is accomplished through the introduction of a new NMR pulse sequence design principle: the triple oscillating field technique. We demonstrate this technique as an efficient means to accomplish broadband dipolar recoupling of homonuclear spins, while decoupling heteronuclear dipolar couplings and anisotropic chemicals shifts and retaining influence from isotropic chemical shifts. In this manner, it possible to synthesize Ising interactions in homonuclear spin networks and thereby avoid dipolar truncation - a serious problem essentially all previous homonuclear dipolar recoupling experiments suffer from. Combination of this recoupling concept with rotor assisted dipolar refocusing enables easy readout of internuclear distances through comparison with analytical Fresnel curves. This forms the basis for a new class of solid-state NMR experiments with potential for structure analysis of uniformly carbon labelled proteins through accurate measurement of {13}C-{13}C internuclear distances. The concept is demonstrated experimentally by measurement of C_alpha-C', C_β-C', and C_γ-C' internuclear distances in powder samples of the amino acids \textit{L}-alanine and \textit{L}-threonine.

quant-ph↗