Optically addressable molecular triplet spins provide a chemically tunable platform for quantum application, but their coherence is often limited by interactions with surrounding spin baths. Here we demonstrate controlled suppression of nuclear-bath-induced decoherence in photoexcited triplet spins of pentacene co-crystallized in high-purity naphthalene single crystals. By hyperpolarizing the proton spin bath through triplet dynamic nuclear polarization (triplet-DNP), magnetic noise generated by the nuclear spins is suppressed, leading to an extension of the electron spin transverse coherence time. Experimentally, we observe a 25\% enhancement of the spin-echo decay time with
60% polarization of the proton spin bath. The measured scaling of the spin-echo decay time (
T2) with nuclear polarization quantitatively follows the predicted dependence derived from the polarization-controlled nuclear second moment. Both the enhancement and the absolute value of the coherence time are quantitatively reproduced by cluster correlation expansion (CCE) simulations. These results establish nuclear spin hyperpolarization as a general and actively tunable approach to engineering coherence in molecular qubits. This work provides a broadly applicable design framework for high-coherence molecular and solid-state spin systems.
The use of nuclear spins as physical sensing systems is disadvantaged by their low signal responsivity, particularly when compared to sensing techniques based on electron spins. This primarily results from the small nuclear gyromagnetic ratio and the difficulties in achieving high spin polarization. Here we develop a new approach to investigating the response of hyperpolarized molecular nuclear spins to magnetic fields and demonstrate orders-of-magnitude enhanced magnetic responsivity over state-of-the-art proton and Overhauser magnetometers. Using hyperpolarized molecules with proton spins, we report the realization of magnetic amplification in linear and nonlinear types. We further extend this amplification to hyperpolarized scalar-coupled multi-spin molecules and observe substantial magnetic amplification exceeding 10%. Moreover, we observe an anomalous amplification with dispersive frequency dependence that originates from magnetic interference effects. Our work highlights the potential of hyperpolarized molecular nuclear spins for use in a new class of quantum sensors, with promising applications in both applied and fundamental physics, including highly accurate absolute magnetometry and the exploration of axion-nucleon exotic interactions.
We study level crossings and spin flips in a system consisting of a spin-1 (an electron spin triplet) coupled to a nuclear spin of arbitrary size
K, in the presence of a uniform magnetic field and the electron spin-spin interaction within the triplet. Through an analytical diagonalization based on the
SU(3) Lie algebra, we find that the electron spin-spin interaction not only removes the curious degeneracy which appears in the absence of the interaction, but also produces some level anticrossings (LACs) for strong interactions. The real-time dynamics of the system shows that periodic spin flips occur at the LACs for arbitrary
K, which might provide an option for nuclear or electron spin polarization.
The goal of this project was to improve our control over nuclear spins in the solid state, and to extend this control to coupled electron-nuclear spins. Our key results are summarized below. 1. We extended the control techniques developed in liquid state NMR quantum information processing to the control of a three-qubit solid state NMR quantum information processor. 2. To explore multi-body spin dynamics and their sensitivity to decoherence, we have measured the decay of NMR multiple quantum coherence intensities in the presence and absence of the dipolar Hamiltonian, in a cubic and a one-dimensional spin system. 3. We also studied the transport of polarization in the one-dimensional fluoroapatite system, both experimentally and theoretically, and created special states in which the polarization is localized to the ends of the chain. This enables both universal Quantum Computing and Quantum Simulation in 1-D systems. 4. We devised a novel scheme for electron-nuclear quantum information processing that exploits the anisotropic hyperfine coupling. This scheme enables universal control over a 1-electron, N-nuclear spin system, addressing only a single electron spin transition. Not having to address the nuclear spins directly significantly speeds up the control. We designed and fabricated a pulsed electron spin resonance spectrometer, along with a cryogenic probe which we used to experimentally implement this scheme on a single crystal sample of irradiated malonic acid. 5. We demonstrated the role of nuclear spin dipolar diffusion in dynamic nuclear polarization (DNP) experiments, in dielectric samples with abundant nuclear spins. We achieved a 29Si polarization of 8.3% at 66 GHz and 1.1 K in single crystal P-doped, the highest ever reported, using DNP.
We theoretically study the interplay of spin-orbit and hyperfine interactions in dynamical nuclear polarization in two-electron semiconductor double quantum dots near the singlet-triplet ($S\ensuremath{-}{T}_{+}$) anticrossing. The goal of the scheme under study is to extend the singlet-triplet ($S\ensuremath{-}{T}_{0}$) qubit decoherence time
T2∗ by dynamically transferring the polarization from the electron spins to the nuclear spins. This polarization transfer is achieved by cycling the electron spins over the $S\ensuremath{-}{T}_{+}$ anticrossing. Here, we investigate, both quantitatively and qualitatively, how this hyperfine-mediated dynamical polarization transfer is influenced by the Rashba and Dresselhaus spin-orbit interaction. In addition to
T2∗, we determine the singlet return probability
Ps, a quantity that can be measured in experiments. Our results suggest that the spin-orbit interaction establishes a mechanism that can polarize the nuclear spins in the direction opposite to that of hyperfine-mediated nuclear spin polarization. In materials with relatively strong spin-orbit coupling, this interplay of spin-orbit and hyperfine-mediated nuclear spin polarizations prevents any notable increase in the $S\ensuremath{-}{T}_{0}$ qubit decoherence time
T2∗.
One-dimensional chains of coupled spins are minimal models of strongly correlated quantum matter, and have been proposed as wires for transporting quantum information. In liquids, rapid molecular tumbling averages anisotropic dipolar couplings and leaves effective isotropic scalar
J-coupling Hamiltonians. At zero- to ultralow-field (ZULF) conditions, differences in frequency between nuclear spins of different types are quenched and the internal Hamiltonians can be closely approximated by an isotropic Heisenberg model. In this work, we present [U-
13C,
15N]-butyronitrile as a chemically engineered nuclear spin chain whose full spin-spin coupling network can be determined and validated by combining high-field NMR detection with evolution at ultralow fields. Starting from high-field (16.4 T) NMR spectra of
1H,
13C, and
15N nuclei, we extract all relevant
J-couplings within a 12-spin network (four
13C, one
15N, and seven
1H). We then employ a mechanical field-cycling apparatus to prepolarize the spins at high field, shuttle them into a magnetically shielded region for evolution at <50 nT, and detect signals after returning to high field. Fourier analysis of the ultralow-field evolution yields indirect
J-spectra that are conceptually analogous to ZULF NMR spectra but measured by a high-field NMR spectrometer. We observe clear spectral features at
J, 1.5
J, and 2
J, in good agreement with simulations using the extracted coupling matrix. Finally, we demonstrate 2D experiments that correlate high-field chemical shifts and, thus, fully map interactions within the molecular spin chain. Our results establish [U-
13C,
15N]-butyronitrile as an extremely well-characterized spin chain model system and provide a quantitative Hamiltonian benchmark for future hyperpolarization and quantum-control studies.