We realize arbitrary-wave-form-based control of spin-selective recombination reactions of radical pairs in the low-magnetic-field regime. To this end, we extend the gradient-ascent pulse engineering (GRAPE) paradigm to allow for optimizing reaction yields. This overcomes drawbacks of previously suggested time-local optimization approaches for the reaction control of radical pairs, which were limited to high biasing fields. We demonstrate how efficient time-global optimization of the recombination yields can be realized by gradient-based methods augmented by time blocking, sparse sampling of the yield, and evaluation of the central single time-step propagators and their Fréchet derivatives using iterated Trotter-Suzuki splittings. Results are shown for both a toy model, previously used to demonstrate coherent control of radical-pair reactions in the simpler high-field scenario and, furthermore, for a realistic exciplex-forming donor-acceptor system comprising 16 nuclear spins. This raises prospects for the spin control of actual radical-pair systems in ambient magnetic fields, by suppressing or boosting radical reaction yields using purpose-specific radio-frequency wave forms, paving the way for reaction-yield-dependent quantum magnetometry and potentially applications of quantum control to biochemical radical-pair reactions. We demonstrate the latter aspect for two radical pairs implicated in quantum biology. Published by the American Physical Society 2024
We realize arbitrary-wave-form-based control of spin-selective recombination reactions of radical pairs in the low-magnetic-field regime. To this end, we extend the gradient-ascent pulse engineering (GRAPE) paradigm to allow for optimizing reaction yields. This overcomes drawbacks of previously suggested time-local optimization approaches for the reaction control of radical pairs, which were limited to high biasing fields. We demonstrate how efficient time-global optimization of the recombination yields can be realized by gradient-based methods augmented by time blocking, sparse sampling of the yield, and evaluation of the central single time-step propagators and their Fréchet derivatives using iterated Trotter-Suzuki splittings. Results are shown for both a toy model, previously used to demonstrate coherent control of radical-pair reactions in the simpler high-field scenario and, furthermore, for a realistic exciplex-forming donor-acceptor system comprising 16 nuclear spins. This raises prospects for the spin control of actual radical-pair systems in ambient magnetic fields, by suppressing or boosting radical reaction yields using purpose-specific radio-frequency wave forms, paving the way for reaction-yield-dependent quantum magnetometry and potentially applications of quantum control to biochemical radical-pair reactions. We demonstrate the latter aspect for two radical pairs implicated in quantum biology. Published by the American Physical Society 2024
The quantum control of spin-correlated radical pairs (SCRPs) holds promise for the targeted manipulation of magnetic field effects (MFEs), with potential applications ranging from the design of noise-resilient quantum information processors to genetically encodable quantum sensors. However, achieving precise handles over the intricate interplay between coherent electron spin dynamics and incoherent relaxation processes in photo-excited radical-pair reactions requires tractable approaches for numerically obtaining controls for large, complex open quantum systems. To that end, we realise optimal control of SCRPs in the low-magnetic-field regime, through first generalising the gradient-ascent pulse engineering (GRAPE) paradigm to allow for optimising time-integral reaction yields for coherent control of SCRP spin dynamics. We then explore how interradical interactions which are unavoidable in a biophysical setting, such as electron-electron dipolar and exchange couplings, alongside driving resulting from intrinsic structural motion, can push the precision of the proposed radical pair quantum compass in cryptochrome closer to approaching the quantum Cram\'{e}r-Rao bound. Remarkably, this approach to optimality is amplified under environmental noise and persists with increasing complexity of the spin system, suggesting that perturbations inherent to such natural systems have enabled them to operate closer to the quantum limit to more effectively extract information from the weak geomagnetic field. Bolstered by these findings, we furthermore demonstrate how a control engineering approach based on the Pontryagin Maximum Principle (PMP) can offer a more computationally feasible route towards realising not only coherent, but also incoherent control, of noisy SCRP open-system spin dynamics. This raises prospects for experimental realisation of spin control of actual radical-pair systems in ambient magnetic fields, by suppressing or boosting radical reaction yields using purpose-specific radio-frequency wave forms, paving the way for inspiring more noise-robust quantum magnetometry via chemical reaction-yield-dependence, and potentially applications of quantum control to physiologically relevant radical-pair reaction intermediates.
The quantum control of spin-correlated radical pairs may enable the targeted manipulation of magnetic field effects, with potential long-term applications across molecular quantum technologies, from prospective noise-resilient quantum information processors to genetically encodable quantum sensors. However, achieving precise handles over the intricate interplay between coherent electron spin dynamics and incoherent relaxation processes in photoexcited radical-pair reactions requires tractable approaches for numerically obtaining controls for large, complex open quantum systems. Employing techniques relying on full Liouville-space propagators to that end becomes computationally infeasible for large spin systems of realistic complexity. Here, we demonstrate how a control engineering approach based on the Pontryagin Maximum Principle (PMP) can offer a viable alternative by reporting on the successful application of PMP-optimal control to steer the coherent and incoherent spin dynamics of noisy radical pairs. This enables controls for prototypical radical-pair models that exhibit robustness in the face of relevant noise sources and paves the way to incoherent control of radical-pair spin dynamics.
This paper aims to devise the shape of the external electromagnetic field that drives the spin dynamics of radical pairs to a quantum coherent state through maximization of the triplet-born singlet yield in biochemical reactions. The model is a Schrödinger system with spin Hamiltonians given by the sum of Zeeman interaction and hyperfine coupling interaction terms. We introduce a one-parameter family of optimal control problems by coupling the Schrödinger system to a control field through filtering equations for the electromagnetic field. Fréchet differentiability and the Pontryagin Maximum Principle in Hilbert space are proved, and the bang-bang structure of the optimal control is established. A new iterative Pontryagin Maximum Principle (IPMP) method for the identification of the bang-bang optimal control is developed. Numerical simulations based on IPMP and the gradient projection method (GPM) in Hilbert spaces are pursued, and the convergence, stability, and the regularization effect are demonstrated. Comparative analysis of filtering with regular optimal electromagnetic field versus non-filtering with bang-bang optimal field ( Abdulla et al, Quantum Sci. Technol., 9 , 4, 2024 ) demonstrates that the change of the maxima of the singlet yield is less than 1%. The results open a venue for a potential experimental work on magnetoreception as a manifestation of quantum biological phenomena.
Zero-field nuclear magnetic resonance (NMR) has been recently developed as a complementary tool for nondestructive structural investigations of matter. However, precise and efficient control in such systems is still at the beginning. Based on the controllability of spin systems, we theoretically study the issue of quantum control in zero-field NMR by using a numerical optimization method based on the gradient ascent pulse engineering (GRAPE) algorithm. A set of quantum gates, including single-qubit and two-qubit gates, are achieved as examples. In particular, we show that homonuclear spins can be individually manipulated in zero-field NMR by the GRAPE method, which extends the ability to manipulate spin systems at zero magnetic field. Quantum control realized by the numerical GRAPE method features the properties of high fidelity, robustness, and hardware-friendly characteristics. High-fidelity quantum control in zero-field NMR systems might provide promising applications in material science, chemical analysis, quantum information processing, and fundamental physics.
An exquisite control over the dynamics of a quantum system is essential for realizing any quantum technology. This thesis presents some practical and efficient strategies for coherent quantum control: a paradigm for controlling quantum dynamics using electromagnetic fields. Coherent control is a common framework for describing the physical implementation of quantum logic gates in several quantum information processing platforms including superconducting qubits and trapped ions. For the purpose of demonstration, however, liquid-state Nuclear Magnetic Resonance (NMR) is used in this thesis as it is an ideal test-bed for developing, testing and benchmarking coherent control tools and techniques. Coherent control was revitalised in 2005 by the development of Gradient Ascent Pulse Engineering (GRAPE), a powerful optimal control technique that is widely used for designing shaped pulses for a variety of tasks. GRAPE, like any other closed-loop optimal control algorithm, requires multiple evaluations of the computationally expensive matrix exponential and the full time-evolution propagator. To this end, I present strategies to sidestep the explicit evaluation of matrix exponentials, thereby offering substantial speed-ups over conventional implementations of the GRAPE algorithm. The results are demonstrated experimentally in NMR, but also in simulations of ultracold molecules and superconducting qubits. Beyond GRAPE, this thesis also considers methods for designing spin-echo sequences for implementing any arbitrary network of controlled-Z gates in a system of qubits with zz-couplings. First, a method based on linear-programming provides near time-optimal sequences in fully-coupled systems having up to a few hundred qubits. Further, an analytic method based on graph colouring finds near time-optimal spin echo sequences in engineered systems with any number of qubits having only nearest and next-nearest neighbour-couplings.
Quantum optimal control, a powerful toolbox for engineering an optimal control field modulation that most precisely implements a desired quantum operation in the best way possible, has evolved into one of the cornerstones for enabling quantum technologies. The gradient ascent pulse engineering (GRAPE) algorithm is a widely used method in quantum optimal control, which has achieved great success in different physical platforms. However, its computational complexity increases exponentially with the number of qubits, making it challenging to be implemented for large-scale quantum systems. To mitigate this issue, we present the iterative GRAPE algorithm (iGRAPE), which reduces the optimization problem into a series of lower-dimensional subproblems by incorporating disentanglement operations. Our numerical simulations on physical platforms such as nuclear magnetic resonance and superconducting quantum systems demonstrate that iGRAPE significantly enhances state preparation speed. Specifically, compared to GRAPE, iGRAPE achieves up to a five-fold acceleration in preparing Greenberger--Horne--Zeilinger states using a 12-qubit implementation, and up to a 13-fold acceleration for arbitrary state preparation with eight qubits. To further validate our findings, we conduct experimental validation of iGRAPE on a four-qubit nuclear magnetic resonance system. Overall, iGRAPE offers an efficient solution for implementing optimal control in large-scale quantum systems, holding great potential for advancing quantum technologies during the noisy intermediate-scale quantum era.