Second Comment on "Spin-selective reactions of radical pairs act as quantum measurements" (Chemical Physics Letters 488 (2010) 90-93)
It is shown that the Jones-Hore theory is either inconsistent or cannot describe single-molecule experiments.
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Publications and source records attributed to I. K. Kominis.
It is shown that the Jones-Hore theory is either inconsistent or cannot describe single-molecule experiments.
In this comment we show that the avian compass entanglement considerations of J. Cai, G. G. Guerreschi and H. J. Briegel (Phys. Rev. Lett. 104, 220502 (2010)) result in unphysical predictions on the magnetic sensitivity of this biochemical sensor. As well known from a series of papers on precision measurements and detailed derivations of standard quantum limits, not taking into account decoherence results in an overestimate of the entanglement lifetime, and this is the case at hand. The entanglement lifetime is wrongly assumed by the authors to be independent of the reaction time (the inverse of the recombination rate) and hence it is grossly overestimated. This is so because the spin coherence lifetime is limited by the reaction time, and the entanglement lifetime cannot be any longer.
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-slit experiment having partial "which-path" information. This analogy directly leads to the general treatment of radical-ion pair reactions covering the whole range between the two extremes, that of perfect singlet-triplet coherence and that of complete incoherence.
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.
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 the effect of deuteration on the reaction yields. Anomalous behavior of radical-ion-pair reactions after deuteration, i.e. data inconsistent with the predictions of the phenomenological theory used so far, has been observed since the 70's and has remained unexplained until now.
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 suppression of spin-exchange relaxation in dense alkali-metal vapors discovered in 1973 and governing modern atomic magnetometers is here reformulated in terms of quantum measurement theory and the quantum Zeno effect. This provides a new perspective of understanding decoherence in spin-polarized atomic vapors.
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. Based on the quantum theory of recombination we will then explain experimental observations incompatible with classical reaction theory, in particular the effect of deuteration on the magnetic sensitivity of radical-ion pair recombination yields.
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 presence. It is here shown that a fundamental quantum phenomenon, the quantum Zeno effect, is at the basis of the radical-ion-pair magnetoreception mechanism. The quantum Zeno effect naturally leads to long spin coherence lifetimes, without any constraints on the systems physical parameters, ensuring the robustness of this sensory mechanism. Basic experimental observations regarding avian magnetic sensitivity are seamlessly derived. These include the magnetic sensitivity functional window and the heading error of oriented bird ensembles, which so far evaded theoretical justification. The findings presented here could be highly relevant to similar mechanisms at work in photosynthetic reactions. They also trigger fundamental questions about the evolutionary mechanisms that enabled avian species to make optimal use of quantum measurement laws.
Spin noise sets fundamental limits to the precision of measurements using spin-polarized atomic vapors, such as performed with sensitive atomic magnetometers. Spin squeezing offers the possibility to extend the measurement precision beyond the standard quantum limit of uncorrelated atoms. Contrary to the current understanding, we show that even in the presence of spin relaxation, spin squeezing can lead to a significant reduction of spin noise, and hence an increase in magnetometric sensitivity, for a long measurement time. This is the case when correlated spin relaxation due to binary alkali-atom collisions dominates independently acting decoherence processes.