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arXiv:0906.5254

Quantum Measurement Theory Explains the Deuteration Effect in Radical-Ion-Pair Reactions

Argyrios T. Dellis, Iannis K. Kominis

Published Jun 29, 2009• 0 citations

Abstract

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.

DOI: 10.48550/arxiv.0906.5254

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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.

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 70s 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-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.

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