Chemical reactions involving radical-ion pairs are ubiquitous in biology, since not only are they at the basis of the photosynthetic reaction chain, but are also assumed to underlie the biochemical magnetic compass used by avian species for navigation. Recent experiments with magnetic-sensitive radical-ion pair reactions provided strong evidence for the radical-ion-pair magnetoreception mechanism, verifying the expected magnetic sensitivities and chemical product yield changes. It is here shown that the theoretical description of radical-ion-pair reactions used since the 70's cannot explain the observed data, because it is based on phenomenological equations masking quantum coherence effects. The fundamental density matrix equation derived here from basic quantum measurement theory considerations naturally incorporates the quantum Zeno effect and readily explains recent experimental observations on low- and high-magnetic-field radical-ion-pair reactions.
Radical-ion pairs are ubiquitous in a wide range of biochemical reactions, ranging from photosynthesis to magnetic sensitive chemical reactions underlying avian magnetic navigation. We here show that the charge recombination of a radical-ion-pair is a continuous quantum measurement process that interrogates the spin state of the pair. This naturally leads to the appearance of the quantum Zeno effect, explaining a large amount of data on unusually long-lived radical-ion-pairs.
The intricate biochemical processes underlying avian magnetoreception, the sensory ability of migratory birds to navigate using earths magnetic field, have been narrowed down to spin-dependent recombination of radical-ion pairs to be found in avian species retinal proteins. The avian magnetic field detection is governed by the interplay between magnetic interactions of the radicals unpaired electrons and the radicals recombination dynamics. Critical to this mechanism is the long lifetime of the radical-pair spin coherence, so that the weak geomagnetic field will have a chance to signal its pre…
Magnetic-sensitive radical-ion-pair reactions are understood to underlie the biochemical magnetic compass used by avian species for navigation. Recent experiments have provided growing evidence for the radical-ion-pair magnetoreception mechanism, while recent theoretical advances have unravelled the quantum nature of radical-ion-pair reactions, which were shown to manifest a host of quantum-information-science concepts and effects, like quantum measurement, quantum jumps and the quantum Zeno effect. We here show that the quantum Zeno effect provides for the robustness of the avian compass mech…
A new paradigm emerging in the description of magnetic-sensitive radical-ion-pair recombination reactions is presented. This paradigm is founded on the realization that the recombination process of radical-ion pairs is a continuous quantum measurement. In the regime of low magnetic fields we describe the appearance of purely quantum phenomena, that fade away as the magnetic field increases. We will analyze the magnetic sensitivity of these reactions under this perspective and bridge the new full quantum theory with the existing classical reaction theory applicable at high magnetic fields. Base…
It has been recently shown that radical-ion pairs and their reactions are a paradigm biological system manifesting non-trivial quantum effects, so far invisible due to the phenomenological description of radical-ion-pair reactions used until now. We here use the quantum-mechanically consistent master equation describing magnetic-sensitive radical-ion-pair reactions to explain experimental data [C. R. Timmel and K. B. Henbest, Phil. Trans. R. Soc. Lond. A {\bf 362}, 2573 (2004); C. T. Rodgers, S. A. Norman, K. B. Henbest, C. R. Timmel and P. J. Hore, J. Am. Chem. Soc. {\bf 129} 6746 (2007)] on …
Chemically induced dynamic nuclear polarization is a ubiquitous phenomenon in photosynthetic reaction centers. The relevant nuclear spin observables are a direct manifestation of the radical-pair mechanism. We here use quantum trajectories to describe the time evolution of radical-pairs, and compare their prediction of nuclear spin observables to the one derived from the radical-pair master equation. While our approach provides a consistent description, we unravel a major inconsistency within the conven- tional theory, thus challenging the theoretical interpretation of numerous CIDNP experimen…
Radical-ion-pair reactions were recently shown to represent a rich biophysical laboratory for the application of quantum measurement theory methods and concepts. We here propose a concrete experimental test that can clearly discriminate among the fundamental master equations currently attempting to describe the quantum dynamics of these reactions. The proposed measurement based on photon statistics of fluorescing radical pairs is shown to be model-independent and capable of elucidating the singlet-triplet decoherence inherent in the radical-ion-pair recombination process.
Radical-ion-pair reactions were recently shown to manifest a host of non-trivial quantum effects accounted for by quantum measurement theory. An alternative approach purporting to describe the fundamental quantum dynamics of spin-selective radical-ion pair reactions was introduced most recently, bringing to three the competing theories, including the one traditionally used in spin chemistry. We here consider entropy as a fundamental concept enabling a comparison of the predictions of these theories against what is physically acceptable on quite general grounds.
The possibility to observe quantum Zeno and anti-Zeno scenarios for atom-diatom reactive collisions is investigated for two diferent processes (F+HD and H+O_2) by means of time-dependent wave packet propagations. A novel approach is proposed in which the survival probabilities investigated are those obtained when the initial state is redefined after time intervals tau at which measurements are performed on the system. The comparison with the actual probability for the unperturbed system reveals the existence of a regime in which the decay from the initial state appears to be inhibited (the qua…
Radical-ion-pair reactions were recently shown to represent a rich biophysical laboratory for the application of quantum measurement theory methods and concepts. We here show that radical-ion-pair reactions essentially form a non-linear biochemical double slit interferometer. Quantum coherence effects are visible when "which-path" information is limited, and the incoherent limit is approached when measurement-induced decoherence sets in. Based on this analogy with the optical double slit experiment we derive and elaborate on the fundamental master equation of spin-selective radical-ion-pair re…
We elaborate on the physical meaning of the non-linear master equation that was recently derived to account for spin-selective radical-ion-pair reactions. Based on quite general arguments, we show that such a non-linear master equation is indeed to be expected.
The yield of chemical reactions involving intermediate radical pairs is influenced by magnetic fields well beyond the levels expected from energy considerations. This dependence can be traced back to the microscopic dynamics of electron spins and constitutes the basis of the chemical compass. Here we propose a new experimental approach based on molecular photoswitches to achieve additional control on the chemical reaction and to allow short-time resolution of the spin dynamics. Our proposal enables experiments to test some of the standard assumptions of the radical pair model and improves the …
Spin-selective reactions of radical pairs have traditionally been modelled theoretically by adding phenomenological rate equations to the quantum mechanical equation of motion of the radical pair spin density matrix. More recently an alternative set of rate expressions, based on a quantum measurement approach, has been suggested. Here we show how these two reaction operators can be seen as limiting cases of a more general reaction scheme.
Radical-ion pairs, fundamental for understanding photosynthesis and the avian magnetic compass, were recently shown to be biological open quantum systems. We here show that the coupling of the radical-pair's spin degrees of freedom to its decohering vibrational reservoir leads to a shift of the radical-pair's magnetic energy levels. The Lamb shift Hamiltonian is diagonal in the singlet-triplet basis, and results in a singlet-triplet energy splitting physically indistinguishable from an exchange interaction. This could have significant implications for understanding the energy level structure a…
A short comment on "The Jones-Hore theory of radical-ion-pair reactions is not self-consistent" (arXiv:1010.3888v3) is presented. In the comment, it is pointed out that the paper includes a misconception about the Jones-Hore approach in Chem. Phys. Lett. 488 (2010) 90-93. The re-formulation is presented and it is demonstrated that the Jones-Hore theory is consistent at least on the point claimed by I. K. Kominis in the paper.
The radical pair reaction underlies the magnetic field sensitivity of chemical reactions and is suggested to play an important role in both chemistry and biology. Current experimental evidence is based on ensemble measurements, however, the ability to probe the radical pair reaction at the single molecule level would provide valuable information concerning its role in important biological processes. Here, we propose a scheme to detect the charge recombination rate in a radical pair reaction under ambient conditions by using single nitrogen-vacancy center spin in diamond. We demonstrate theoret…
We adapt the Monte-Carlo wavefunction (MCWF) approach to treat the open-system spin dynamics of radical pairs subject to spin-selective recombination reactions. For these systems, non-Lindbladian master equations are widely employed, which account for recombination via the non trace-preserving Haberkorn superoperator in combination with reaction-dependent exchange and singlet-triplet dephasing terms. We show that this type of master equation can be accommodated in the MCWF approach, by introducing a second type of quantum jump that accounts for the reaction simply by suitably terminating the p…
Classical chemical kinetics use rate-equation models to describe how a reaction proceeds in time. Such models are sufficient for describing state transitions in a reaction where coherences between different states do not arise, or in other words, a reaction which contain only incoherent transitions. A prominent example reaction containing coherent transitions is the radical-pair model. The kinetics of such reactions is defined by the so-called reaction operator which determines the radical-pair state as a function of intermediate transition rates. We argue that the well-known concept of quantu…
Radical-ion-pair reactions were recently shown to represent a rich biophysical laboratory for the application of quantum measurement theory methods and concepts, casting doubt on the validity of the theoretical treatment of these reactions and the results thereof that has been at the core of spin chemistry for several decades now. The ensued scientific debate, although exciting, is plagued with several misconceptions. We will here provide a comprehensive treatment of the quantum dynamics of radical-ion-pair reactions, generalizing our recent work and elaborating on the analogy with the double-…
A popular hypothesis ascribes magnetoreception to a magnetosensitive recombination reaction of a pair of radicals in the protein cryptochrome. Many theoretical studies of this model have ignored inter-radical interactions, particularly the electron-electron dipolar coupling (EED), which have a detrimental effect on the magnetosensitivity. Here, we set out to elucidate if a radical pair allowed to undergo internal motion can yield enhanced magneto-sensitivity. Our model considers the effects of diffusive motion of one radical partner along a one-dimensional reaction coordinate. Such dynamics co…
Since the 1970s, spin-selective reactions of radical pairs have been modelled theoretically by adding phenomenological rate equations to the quantum mechanical equation of motion of the radical pair spin density matrix. Here, using a quantum measurement approach, we derive an alternative set of rate expressions which predict a faster decay of coherent superpositions of the singlet and triplet radical pair states. The difference between the two results, however, is not dramatic and would probably be difficult to distinguish experimentally from decoherence arising from other sources.
We apply the quantum-walk approach recently proposed in arXiv:quant-ph-1506.04213 to a radical-pair reaction where realistic estimates for the intermediate transition rates are available. The well-known average hitting time from quantum walks can be adopted as a measure of how quickly the reaction occurs and we calculate this for varying degrees of dephasing in the radical pair. The time for the radical pair to react to a product is found to be independent of the amount of dephasing introduced, even in the limit of no dephasing where the transient population dynamics exhibit strong coherent os…
Recently, spin-selective radical pair reactions have been studied using concepts from quantum measurement theory. In this Article, we show that the approach taken by Kominis (Physical Review E, 83, 2011, 056118) leads to erroneous results due to a problematic treatment of quantum jumps. Correct consideration of quantum jumps leads to either the traditional master equation or the Jones-Hore master equation.
In his Comment on a recent paper by two of us Kominis claims that the recently proposed quantum measurement model for spin-selective reactions of radical pairs leads to ambiguous predictions in a simple case. Here we show that this claim is based on a confusion between the unreacted and unrecombined portions of the radical pairs, and to an incorrect interpretation of the improper density matrices used in both our model and the conventional Haberkorn model of such reactions. We further show that if this error is corrected then the supposed ambiguity is resolved.
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 magnetomete…
Radical-ion-pair reactions, central for understanding the avian magnetic compass and spin transport in photosynthetic reaction centers, were recently shown to be a fruitful paradigm of the new synthesis of quantum information science with biological processes. We show here that the master equation so far constituting the theoretical foundation of spin chemistry violates fundamental bounds for the entropy of quantum systems, in particular the Ozawa bound. In contrast, a recently developed theory based on quantum measurements, quantum coherence measures, and quantum retrodiction, thus exemplifyi…
We formulate a multiple-encounter model of the radical pair mechanism that is based on a random coupling of the radical pair to a minimal model environment. These occasional pulse-like couplings correspond to the radical encounters and give rise to both dephasing and recombination. While this is in agreement with the original model of Haberkorn and its extensions that assume additional dephasing, we show how a nonlinear master equation may be constructed to describe the conditional evolution of the radical pairs prior to the detection of their recombination. We propose a nonlinear master equat…
The radical-pair mechanism was introduced in the 1960's to explain anomalously large EPR and NMR signals in chemical reactions of organic molecules. It has evolved to the cornerstone of spin chemistry, the study of the effect electron and nuclear spins have on chemical reactions, with the avian magnetic compass mechanism and the photosynthetic reaction center dynamics being prominent biophysical manifestations of such effects. In recent years the radical-pair mechanism was shown to be an ideal biological system where the conceptual tools of quantum information science can be fruitfully applied…
Magnetic field effects (MFE) in certain chemical reactions have been well established in the last five decades and are attributed to the evolution of transient radical-pairs whose spin dynamics are determined by local and external magnetic fields. The majority of existing experimental techniques used to probe these reactions only provide ensemble averaged reaction parameters and spin chemistry, hindering the observation of the potential presence of quantum coherent phenomena at the single molecule scale. Here, considering a single nitrogen vacancy (NV) centre as quantum sensor, we investigate …
Adult hippocampal neurogenesis and hippocampus-dependent cognition in mice have been found to be adversely affected by hypomagnetic field exposure. The effect concurred with a reduction of reactive oxygen species in the absence of the geomagnetic field. A recent theoretic study suggests a mechanistic interpretation of this phenomenon in the framework of the Radical Pair Mechanism. According to this model, a flavin-superoxide radical pair, born in the singlet spin configuration, undergoes magnetic field-dependent spin dynamics such that the pair's recombination is enhanced as the applied magnet…
Radical-ion-pair reactions, central in photosynthesis and the avian magnetic compass mechanism, have recently shown to be a paradigm system for applying quantum information science in a biochemical setting. The fundamental quantum master equation describing radical-ion-pair reactions is still under debate. We here use quantum retrodiction to produce a rigorous refinement of the theory put forward in Phys. Rev. E {\bf 83}, 056118 (2011). We also provide a rigorous analysis of the measure of singlet-triplet coherence required for deriving the radical-pair master equation. A Monte-Carlo simulatio…
A quantum-based magnetic compass sensor, mediated through radical pair reactions, has been suggested to underlie the sensory ability of migrating birds to receive directional information from the geomagnetic field. Here we extend the currently available models by considering the effects of slow fluctuations in the nuclear spin environment on the directional signal. We quantitatively evaluate the robustness of signals under fluctuations on a timescale longer than the lifetime of a radical pair, utilizing two models of radical pairs. Our results suggest design principles for building a radical-p…
Chemically induced dynamic nuclear polarization is a signature of spin order appearing in many photosynthetic reaction centers. Such polarization, significantly enhanced above thermal equilibrium, is known to result from the nuclear spin sorting inherent in the radical pair mechanism underlying long-lived charge-separated states in photosynthetic reaction centers. We will here show that the recently understood fundamental quantum dynamics of radical-ion-pair reactions open up a new and completely unexpected venue towards obtaining CIDNP signals. The fundamental decoherence mechanism inherent i…
We review the spin radical pair mechanism which is a promising explanation of avian navigation. This mechanism is based on the dependence of product yields on (1) the hyperfine interaction involving electron spins and neighboring nuclear spins and (2) the intensity and orientation of the geomagnetic field. One surprising result is that even at ambient conditions quantum entanglement of electron spins can play an important role in avian magnetoreception. This review describes the general scheme of chemical reactions involving radical pairs generated from singlet and triplet precursors; the spin…
We present and analyze a toolbox for the controlled manipulation of ultracold polar molecules, consisting of detection of molecules, atom-molecule entanglement, and engineering of dissipative dynamics. Our setup is based on fast chemical reactions between molecules and atoms leading to a quantum Zeno-based collisional blockade in the system. We demonstrate that the experimental parameters for achieving high fidelities can be found using a straightforward numerical optimization. We exemplify our approach for a system comprised of NaK molecules and Na atoms and we discuss the consequences of res…
Towards Application of Nanodiamonds for in-situ Monitoring of Radicals in Liquid Phase Chemical Reactions
RPTU University（莱布尼茨技术大学）；State Research Center OPTIMAS, RPTU University（OPTIMAS州立研究中心，莱布尼茨技术大学）；Kiel University（基尔大学）；Kiel Nano, Surface and Interface Science (KiNSIS), Kiel University（基尔纳米、表面与界面科学研究所（KiNSIS），基尔大学）
The Radical Pair Mechanism is a canonical model for the magnetosensitivity of chemical reaction processes. The key ingredient of this model is the hyperfine interaction that induces a coherent mixing of singlet and triplet electron spin states in pairs of radicals, thereby facilitating magnetic field effects (MFEs) on reaction yields through spin-selective reaction channels. We show that the hyperfine interaction is not a categorical requirement to realize the sensitivity of radical reactions to weak magnetic fields. We propose that, in systems comprising three instead of two radicals, dipolar…
Birds have a remarkable ability to obtain navigational information from the Earth's magnetic field. The primary detection mechanism of this compass sense is uncertain but appears to involve the quantum spin dynamics of radical pairs formed transiently in cryptochrome proteins. We propose here a new version of the current model in which spin-selective recombination of the radical pair is not essential. One of the two radicals is imagined to react with a paramagnetic scavenger via spin-selective electron transfer. By means of simulations of the spin dynamics of cryptochrome-inspired radical pair…
We present the quantum limits to the magnetic sensitivity of a new kind of magnetometer based on biochemical reactions. Radical-ion-pair reactions, the biochemical system underlying the chemical compass, are shown to offer a new and unique physical realization of a magnetic field sensor competitive to modern atomic or condensed matter magnetometers. We elaborate on the quantum coherence and entanglement dynamics of this sensor, showing that they provide the physical basis for testing our understanding of the fundamental quantum dynamics of radical-ion-pair reactions.
The so-called "phenomenological" kinetic equation for one-pair density operator for spin-selective reactions is defended. We derive this equation from the kinetic equation for density operator of all pairs which are treated as singlet and triplet bosons. There presented some reasons for inconsistency of measurement-like approach to the problem.
In theories of spin-dependent radical pair reactions, the time evolution of the radical pair, including the effect of the chemical kinetics, is described by a master equation in the Liouville formalism. For the description of the chemical kinetics, a number of possible reaction operators have been formulated in the literature. In this work, we present a framework that allows for a unified description of the various proposed mechanisms and the forms of reaction operators for the spin-selective recombination processes. Based on the concept that master equations can be derived from a microscopic …
Near-zero magnetic fields, called hypomagnetic fields, are known to impact biological phenomena, including developmental processes, the circadian system, neuronal and brain activities, DNA methylation, calcium balance in cells, and many more. However, the exact mechanism underlying such effects is still elusive, as the corresponding energies are far smaller than thermal energies. It is known that chemical reactions involving radical pairs can be magnetic field dependent at very low intensities comparable to or less than the geomagnetic field. Here, we review in detail hypomagnetic field effect…
Radical-pair reactions pertinent to biological magnetic field sensing are an ideal system for demonstrating the paradigm of quantum biology, the exploration of quantum coherene effects in complex biological systems. We here provide yet another fundamental connection between this biochemical spin system and quantum information science. We introduce and explore a formal measure quantifying singlet-triplet coherence of radical-pairs using the concept of quantum relative entropy. The ability to quantify singlet-triplet coherence opens up a number of possibilities in the study of magnetic sensing w…
The exact mechanism behind general anesthesia remains an open question in neuroscience. It has been proposed that anesthetics selectively prevent consciousness and memory via acting on microtubules (MTs). It is known that the magnetic field modulates MT organization. A recent study shows that a radical pair model can explain the isotope effect in xenon-induced anesthesia and predicts magnetic field effects on anesthetic potency. Further, reactive oxygen species are also implicated in MT stability and anesthesia. Based on a simple radical pair mechanism model and a simple mathematical model of …
We investigate the physical meaning of quantum superposition states between reactants and products in electron transfer reactions. We show that such superpositions are strongly suppressed and to leading orders of perturbation theory do not pertain in electron transfer reactions. This is because of the intermediate manifold of states separating the reactants from the products. We provide an intuitive description of these considerations with Feynman diagrams. We also discuss the relation of such quantum coherences to understanding the fundamental quantum dynamics of spin-selective radical-ion-pa…
The mechanism of avian navigation is an important question for global scientists. One of the most famous candidates is the radical pair mechanism (RPM), which shows that avian navigation is achieved by detecting the amount of products from chemical reactions, which exhibit different properties for singlet and triplet spin states. Based on the theory, we explore the amount of the the singlet recombination product by changing the coupling strength and direction of the magnetic field. The radical pair in our model is coupled with a Lipkin-Meshkov-Glick (LMG) bath, which proposes attractive result…
We investigate theoretically the suppression of two-body losses when the on-site loss rate is larger than all other energy scales in a lattice. This work quantitatively explains the recently observed suppression of chemical reactions between two rotational states of fermionic KRb molecules confined in one-dimensional tubes with a weak lattice along the tubes [Yan et al., Nature 501, 521-525 (2013)]. New loss rate measurements performed for different lattice parameters but under controlled initial conditions allow us to show that the loss suppression is a consequence of the combined effects of …
Magnetic fields as weak as Earth's may affect the outcome of certain photochemical reactions that go through a radical pair intermediate. When the reaction environment is anisotropic, this phenomenon can form the basis of a chemical compass and has been proposed as a mechanism for animal magnetoreception. Here, we demonstrate how to optimize the design of a chemical compass with a much better directional sensitivity simply by a gradient field, e.g. from a magnetic nanostructure. We propose an experimental test of these predictions, and suggest design principles for a hybrid metallic-organic ch…
