Entanglement and Sources of Magnetic Anisotropy in Radical Pair-Based Avian Magnetoreceptors

One of the principal models of magnetic sensing in migratory birds rests on the quantum spin-dynamics of transient radical pairs created photochemically in ocular cryptochrome proteins. We consider here the role of electron spin entanglement and coherence in determining the sensitivity of a radical pair-based geomagnetic compass and the origins of the directional response. It emerges that the anisotropy of radical pairs formed from spin-polarized molecular triplets could form the basis of a more sensitive compass sensor than one founded on the conventional hyperfine-anisotropy model. This property offers new and more flexible opportunities for the design of biologically inspired magnetic compass sensors

Asymmetric recombination and electron spin relaxation in the semiclassical theory of radical pair reactions

We describe how the semiclassical theory of radical pair recombination reactions recently introduced by two of us [D. E. Manolopoulos and P. J. Hore, J. Chem. Phys. 139, 124106 (2013)] can be generalised to allow for different singlet and triplet recombination rates. This is a non-trivial generalisation because when the recombination rates are different the recombination process is dynamically coupled to the coherent electron spin dynamics of the radical pair. Furthermore, because the recombination operator is a two-electron operator, it is no longer sufficient simply to consider the two electrons as classical vectors: one has to consider the complete set of 16 two-electron spin operators as independent classical variables. The resulting semiclassical theory is first validated by comparison with exact quantum mechanical results for a model radical pair containing 12 nuclear spins. It is then used to shed light on the spin dynamics of a carotenoid-porphyrin-fullerene (CPF) triad containing considerably more nuclear spins which has recently been used to establish a 'proof of principle' for the operation of a chemical compass [K. Maeda et al., Nature 453, 387 (2008)]. We find in particular that the intriguing biphasic behaviour that has been observed in the effect of an Earth-strength magnetic field on the time-dependent survival probability of the photo-excited C+PF- radical pair arises from a delicate balance between its asymmetric recombination and the relaxation of the electron spin in the carotenoid radical

Time evolution of spin state of radical ion pair in microwave field: An analytical solution

The paper reports an exact solution for the problem of spin evolution of radical ion pair in static magnetic and resonant microwave field taking into account Zeeman and hyperfine interactions and spin relaxation. The values of parameters that provide one of the four possible types of solution are analysed. It is demonstrated that in the absence of spin relaxation, besides the zero field invariant an invariant at large amplitudes of the resonant microwave field can be found. The two invariants open the possibility for simple calculation of microwave pulses to control quantum state of the radical pair. The effect of relaxation on the invariants is analysed and it is shown that changes in the high field invariant are induced by phase relaxation.Comment: 18 pages, 7 figure

Electron spin relaxation can enhance the performance of a cryptochrome-based magnetic compass sensor

The radical pair model of the avian magnetoreceptor relies on long‐lived electron spin coherence. Dephasing, resulting from interactions of the spins with their fluctuating environment, is generally assumed to degrade the sensitivity of this compass to the direction of the Earth's magnetic field. Here we argue that certain spin relaxation mechanisms can enhance its performance. We focus on the flavin‐tryptophan radical pair in cryptochrome, currently the only candidate magnetoreceptor molecule. Correlation functions for fluctuations in the distance between the two radicals in Arabidopsis thaliana cryptochrome 1 were obtained from molecular dynamics simulations and used to calculate the spin relaxation caused by modulation of the exchange and dipolar interactions. We find that intermediate spin relaxation rates afford substantial enhancements in the sensitivity of the reaction yields to an Earth‐strength magnetic field. Supported by calculations using toy radical pair models, we argue that these enhancements could be consistent with the molecular dynamics and magnetic interactions in avian cryptochromes

Fluorescence-detected magnetic field effects on radical pair reactions from femtolitre volumes

We show that the effects of applied magnetic fields on radical pair reactions can be sensitively measured from sample volumes as low as ~100 femtolitres using total internal reflection fluorescence microscopy. Development of a fluorescence-based microscope method is likely to be a key step in further miniaturisation that will allow detection of magnetic field effects on single molecules

Bird Cryptochrome 1a Is Excited by Blue Light and Forms Long-Lived Radical- Pairs

Cryptochromes (Cry) have been suggested to form the basis of light-dependent magnetic compass orientation in birds. However, to function as magnetic compass sensors, the cryptochromes of migratory birds must possess a number of key biophysical characteristics. Most importantly, absorption of blue light must produce radical pairs with lifetimes longer than about a microsecond. Cryptochrome 1a (gwCry1a) and the photolyase-homology-region of Cry1 (gwCry1-PHR) from the migratory garden warbler were recombinantly expressed and purified from a baculovirus/Sf9 cell expression system. Transient absorption measurements show that these flavoproteins are indeed excited by light in the blue spectral range leading to the formation of radicals with millisecond lifetimes. These biophysical characteristics suggest that gwCry1a is ideally suited as a primary light-mediated, radical-pair-based magnetic compass recepto

Implementation of NMR quantum computation with para-hydrogen derived high purity quantum states

We demonstrate the first implementation of a quantum algorithm on a liquid state nuclear magnetic resonance (NMR) quantum computer using almost pure states. This was achieved using a two qubit device where the initial state is an almost pure singlet nuclear spin state of a pair of 1H nuclei arising from a chemical reaction involving para-hydrogen. We have implemented Deutsch's algorithm for distinguishing between constant and balanced functions with a single query.Comment: 7 pages RevTex including 6 figures. Figures 4-6 are low quality to save space. Submitted to Phys Rev

On the Ground State of Electron Gases at Negative Compressibility

Two- and three-dimensional electron gases with a uniform neutralizing background are studied at negative compressibility. Parametrized expressions for the dielectric function are used to access this strong-coupling regime, where the screened Coulomb potential becomes overall attractive for like charges. Closely examining these expressions reveals that the ground state with a periodic modulation of the charge density, albeit exponentially damped, replaces the homogeneous one at positive compressibility. The wavevector characterizing the new ground state depends on the density and is complex, having a positive imaginary part, as does the homogeneous ground state, and real part, as does the genuine charge density wave.Comment: 6 double-column pages, 2 figures. 2nd version is an extension of the 1st one, giving more detail

Approximate Quantum Cloning with Nuclear Magnetic Resonance

Here we describe a Nuclear Magnetic Resonance (NMR) experiment that uses a three qubit NMR device to implement the one to two approximate quantum cloning network of Buzek et al.Comment: 4 pages RevTeX4 including 5 postscript figures. Submitted to PR

Copper-Mediated Amidation of Heterocyclic and Aromatic C−H Bonds

A copper-mediated aerobic coupling reaction enables direct amidation of heterocycles or aromatics having weakly acidic C−H bonds with a variety of nitrogen nucleophiles. These reactions provide efficient access to many biologically important skeletons, including ones with the potential to serve as inhibitors of HMTs.Chemistry and Chemical Biolog