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Should recombinations of radical pairs be considered as accompanied by measurements?

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 Added by Sergey Anishchik
 Publication date 2010
  fields Physics
and research's language is English




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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.



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We address the problem of relative frequencies of singlet and triplet recombinations in a multiparticle system, which consists of spin-correlated radical ion pairs. The nonlocal swapping of spin correlations due to cross-recombinations is taken into account. It is shown that this swapping does not contribute to singlet and triplet recombination frequencies in the absence of spin evolution in the correlated pairs.
We show that the stochastic Schrodinger equation (SSE) provides an ideal way to simulate the quantum mechanical spin dynamics of radical pairs. Electron spin relaxation effects arising from fluctuations in the spin Hamiltonian are straightforward to include in this approach, and their treatment can be combined with a highly efficient stochastic evaluation of the trace over nuclear spin states that is required to compute experimental observables. These features are illustrated in example applications to a flavin-tryptophan radical pair of interest in avian magnetoreception, and to a problem involving spin-selective radical pair recombination along a molecular wire. In the first of these examples, the SSE is shown to be both more efficient and more widely applicable than a recent stochastic implementation of the Lindblad equation, which only provides a valid treatment of relaxation in the extreme-narrowing limit. In the second, the exact SSE results are used to assess the accuracy of a recently-proposed combination of Nakajima-Zwanzig theory for the spin relaxation and Schulten-Wolynes theory for the spin dynamics, which is applicable to radical pairs with many more nuclear spins. An appendix analyses the efficiency of trace sampling in some detail, highlighting the particular advantages of sampling with SU(N) coherent states.
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