Navigating at night: fundamental limits on the sensitivity of radical pair magnetoreception under dim light.

Night-migratory songbirds appear to sense the direction of the Earth's magnetic field via radical pair intermediates formed photochemically in cryptochrome flavoproteins contained in photoreceptor cells in their retinas. It is an open question whether this light-dependent mechanism could be sufficiently sensitive given the low-light levels experienced by nocturnal migrants. The scarcity of available photons results in significant uncertainty in the signal generated by the magnetoreceptors distributed around the retina. Here we use results from Information Theory to obtain a lower bound estimate of the precision with which a bird could orient itself using only geomagnetic cues. Our approach bypasses the current lack of knowledge about magnetic signal transduction and processing in vivo by computing the best-case compass precision under conditions where photons are in short supply. We use this method to assess the performance of three plausible cryptochrome-derived flavin-containing radical pairs as potential magnetoreceptors.

An improved semiclassical theory of radical pair recombination reactions.

We present a practical semiclassical method for computing the electron spin dynamics of a radical in which the electron spin is hyperfine coupled to a large number of nuclear spins. This can be used to calculate the singlet and triplet survival probabilities and quantum yields of radical recombination reactions in the presence of magnetic fields. Our method differs from the early semiclassical theory of Schulten and Wolynes [J. Chem. Phys. 68, 3292 (1978)] in allowing each individual nuclear spin to precess around the electron spin, rather than assuming that the hyperfine coupling-weighted sum of nuclear spin vectors is fixed in space. The downside of removing this assumption is that one can no longer obtain a simple closed-form expression for the electron spin correlation tensor: our method requires a numerical calculation. However, the computational effort increases only linearly with the number of nuclear spins, rather than exponentially as in an exact quantum mechanical calculation. The method is therefore applicable to arbitrarily large radicals. Moreover, it approaches quantitative agreement with quantum mechanics as the number of nuclear spins increases and the environment of the electron spin becomes more complex, owing to the rapid quantum decoherence in complex systems. Unlike the Schulten-Wolynes theory, the present semiclassical theory predicts the correct long-time behaviour of the electron spin correlation tensor, and it therefore correctly captures the low magnetic field effect in the singlet yield of a radical recombination reaction with a slow recombination rate.

A statistical quasiclassical trajectory model for atom-diatom insertion reactions.

A statistical model based on the quasiclassical trajectory method is presented in this work for atom-diatom insertion reactions. The basic difference between this and the corresponding statistical quantum model (SQM) lies in the fact that trajectories instead of wave functions are propagated in the entrance and exit channels. Other than this the two formulations are entirely similar. In particular, it is shown that conservation of parity can be taken into account in a natural and precise way in the statistical quasiclassical trajectory (SQCT) model. Additionally, the SQCT model complies with the principle of detailed balance and overcomes the problem of the zero point energy in the products. As a test, the model is applied to the H3+ and H+D2 exchange reactions. The excellent agreement between the SQCT and SQM results, especially in the case of the differential cross sections, indicates that the effect of tunneling through the centrifugal barrier is negligible. The effect of ignoring quantum mechanical parity conservation is also investigated.

The transition state of the f + h2 reaction.

The transition state region of the F + H(2) reaction has been studied by photoelectron spectroscopy of FH(2)(-). New para and normal FH(2)(-)photoelectron spectra have been measured in refined experiments and are compared here with exact three-dimensional quantum reactive scattering simulations that use an accurate new ab initio potential energy surface for F + H(2). The detailed agreement that is obtained between this fully ab initio theory and experiment is unprecedented for the F + H(2) reaction and suggests that the transition state region of the F + H(2) potential energy surface has finally been understood quantitatively.