Abstract Optimal control of the external electromagnetic field input for the maximization of the quantum triplet-singlet yield of the radical pairs in biochemical reactions modeled by Schrödinger system with spin Hamiltonians given by the sum of Zeeman interaction and hyperfine coupling interaction terms are analyzed. Fréchet differentiability and Pontryagin Maximum Principle in Hilbert space is proved and the bang-bang structure of the optimal control is established. A closed optimality system of nonlinear differential equations for the identification of the bang-bang optimal control is revealed. Numerical methods for the identification of the bang-bang optimal control based on the Pontryagin maximum principle are developed. Numerical simulations are pursued, and the convergence and stability of the numerical methods are demonstrated. The results contribute towards understanding the structure-function relationship of the putative magnetoreceptor to manipulate and enhance quantum coherences at room temperature and leveraging biofidelic function to inspire novel quantum devices.
Abstract Optimal control of the external electromagnetic field input for the maximization of the quantum triplet-singlet yield of the radical pairs in biochemical reactions modeled by Schrödinger system with spin Hamiltonians given by the sum of Zeeman interaction and hyperfine coupling interaction terms are analyzed. Fréchet differentiability and Pontryagin Maximum Principle in Hilbert space is proved and the bang-bang structure of the optimal control is established. A closed optimality system of nonlinear differential equations for the identification of the bang-bang optimal control is revealed. Numerical methods for the identification of the bang-bang optimal control based on the Pontryagin maximum principle are developed. Numerical simulations are pursued, and the convergence and stability of the numerical methods are demonstrated. The results contribute towards understanding the structure-function relationship of the putative magnetoreceptor to manipulate and enhance quantum coherences at room temperature and leveraging biofidelic function to inspire novel quantum devices.
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.
Identification of the external electromagnetic fields and internal hyperfine parameters which optimize the quantum singlet-triplet yield of simplified radical pairs modeled by Schrödinger system with spin Hamiltonians given by the sum of Zeeman interaction and hyperfine coupling interaction terms are analyzed. A method that combines sensitivity analysis with Tikhonov regularization is implemented. Numerical results demonstrate that the quantum singlet-triplet yield of the radical pair system can be significantly reduced if optimization is pursued simultaneously for both external magnetic fields and internal hyperfine parameters. The results may contribute towards understanding the structure-function relationship of a putative magnetoreceptor to manipulate and enhance quantum coherences at room temperature and leveraging biofidelic function to inspire novel quantum devices.
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.
Using the Pontryagin maximum principle, the generic structure of optimal policies is deduced for typical quantum control tasks involving coherent lasers, magnetic fields and reservoir engineering. In addition, the periodic optimization is considered for the first time in view of prospective applications. We proved that nearly all optimal policies are actively constrained by technical bounds on control parameter but reduce to entirely bang-bang sequences only in special cases, such as the environmental control by random collisions. The results allow to arguably refute two generally accepted and concurring conjectures regarding the structure of optimal controls.
Radical-ion pairs and their reactions have triggered the study of quantum effects in biological systems. This is because they exhibit a number of effects best understood within quantum information science, and at the same time are central in understanding the avian magnetic compass and the spin transport dynamics in photosynthetic reaction centers. Here we address radical-pair reactions from the perspective of quantum metrology. Since the coherent spin motion of radical pairs is effected by an external magnetic field, these spin-dependent reactions essentially realize a biochemical magnetometer. Using the quantum Fisher information, we find the fundamental quantum limits to the magnetic sensitivity of radical-pair magnetometers, arriving at a sensitivity $\ensuremath{\delta}B=2\phantom{\rule{0.16em}{0ex}}\mathrm{pT}/\ensuremath{\tau}[1\phantom{\rule{0.16em}{0ex}}\ensuremath{\mu}\text{s}]\sqrt{{\ensuremath{\nu}}_{0}[{10}^{12}]}$, given in terms of radical-pair lifetime $\ensuremath{\tau}$ and number of radical pairs ${\ensuremath{\nu}}_{0}$. We then explore how well the usual measurement scheme considered in radical-pair reactions, the measurement of reaction yields, approaches the fundamental limits. In doing so, we find the optimal hyperfine interaction Hamiltonian that leads to the best magnetic sensitivity as obtained from reaction yields. This is still an order of magnitude smaller than the absolute quantum limit. Finally, we demonstrate that with a realistic quantum reaction control reminding one of Ramsey interferometry, here presented as a quantum circuit involving the spin-exchange interaction and a recently proposed molecular switch, we can approach the fundamental quantum limit within a factor of 2. This work opens the application of well-advanced quantum metrology methods to biological systems.