We present the quantum limits to the magnetic sensitivity of a new kind of magnetometer based on biochemical reactions. Radical-ion-pair reactions, the biochemical system underlying the chemical compass, are shown to offer a new and unique physical realization of a magnetic field sensor competitive to modern atomic or condensed matter magnetometers. We elaborate on the quantum coherence and entanglement dynamics of this sensor, showing that they provide the physical basis for testing our understanding of the fundamental quantum dynamics of radical-ion-pair reactions.
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 …
It is known that more than 50 species use the Earth's magnetic field for orientation and navigation. Intensive studies particularly behavior experiments with birds, provide support for a chemical compass based on magnetically sensitive free radical reactions as a source of this sense. However, the fundamental question of how quantum coherence plays an essential role in such a chemical compass model of avian magnetoreception yet remains controversial. Here, we show that the essence of the chemical compass model can be understood in analogy to a quantum interferometer exploiting global quantum c…
The Radical Pair Mechanism can help to explain avian orientation and navigation. Some evidence indicates that the intensity of external magnetic fields plays an important role in avian navigation. In this paper, based on a two-stage strategy, we demonstrate that birds could reasonably detect the directions of geomagnetic fields and gradients of these fields using a yield-based chemical compass that is sensitive enough for navigation. Also, we find that the lifetime of entanglement in this proposed compass is angle-dependent and long enough to allow adequate electron transfer between molecules.
The chemical compass model, based on radical pair reactions, is a fascinating idea to explain avian magnetoreception. At present, questions concerning the key ingredients responsible for the high sensitivity of a chemical compass and the possible role of quantum coherence and decoherence remain unsolved. Here, we investigate the optimized hyperfine coupling for a chemical compass in order to achieve the best magnetic field sensitivity. We show that its magnetic sensitivity limit can be further extended by simple quantum control and may benefit from additional decoherence. With this, we clearly…
We review the spin radical pair mechanism which is a promising explanation of avian navigation. This mechanism is based on the dependence of product yields on (1) the hyperfine interaction involving electron spins and neighboring nuclear spins and (2) the intensity and orientation of the geomagnetic field. One surprising result is that even at ambient conditions quantum entanglement of electron spins can play an important role in avian magnetoreception. This review describes the general scheme of chemical reactions involving radical pairs generated from singlet and triplet precursors; the spin…
Magnetic fields as weak as Earth's may affect the outcome of certain photochemical reactions that go through a radical pair intermediate. When the reaction environment is anisotropic, this phenomenon can form the basis of a chemical compass and has been proposed as a mechanism for animal magnetoreception. Here, we demonstrate how to optimize the design of a chemical compass with a much better directional sensitivity simply by a gradient field, e.g. from a magnetic nanostructure. We propose an experimental test of these predictions, and suggest design principles for a hybrid metallic-organic ch…
Contrary to the usual picture that decoherence destroys quantum properties and causes the quantum-to-classical transition, we argue that decoherence can also play a constructive role in driving quantum dynamics and amplifying its results to macroscopic scales. We support this perspective by presenting an example system from spin chemistry, which is also of importance for biological systems, e.g. in avian magnetoreception.
In artificial systems, quantum superposition and entanglement typically decay rapidly unless cryogenic temperatures are used. Could life have evolved to exploit such delicate phenomena? Certain migratory birds have the ability to sense very subtle variations in Earth's magnetic field. Here we apply quantum information theory and the widely accepted "radical pair" model to analyze recent experimental observations of the avian compass. We find that superposition and entanglement are sustained in this living system for at least tens of microseconds, exceeding the durations achieved in the best co…
We review the consequences of intrinsic frustration of the orbital superexchange and of spin-orbital entanglement. While Heisenberg perturbing interactions remove frustration in the compass model, the lowest columnar excitations are robust in the nanoscopic compass clusters and might be used for quantum computations. Entangled spin-orbital states determine the ground states in some cases, while in others concern excited states and lead to measurable consequences, as in the $R$VO$_3$ perovskites. On-site entanglement for strong spin-orbit coupling generates the frustrated Kitaev-Heisenberg mode…
The radical pair mechanism is one of the two main hypotheses to explain the navigability of animals in weak magnetic fields, enabling e.g. birds to see the Earth's magnetic field. It also plays an essential role in the field of spin chemistry. Here, we show how quantum control can be used to either enhance or reduce the performance of such a chemical compass, providing a new route to further study the radical pair mechanism and its applications. We study the role of quantum entanglement in this mechanism, and demonstrate intriguing connections between radical-pair entanglement and the magnetic…
We propose a new approach to the geometry of the four-qubit entanglement classes depending on parameters. More precisely, we use invariant theory and algebraic geometry to describe various stratifications of the Hilbert space by SLOCC invariant algebraic varieties. The normal forms of the four-qubit classification of Verstraete {\em et al.} are interpreted as dense subsets of components of the dual variety of the set of separable states and an algorithm based on the invariants/covariants of the four-qubit quantum states is proposed to identify a state with a SLOCC equivalent normal form (up to…
The radical pair mechanism is one of two distinct mechanisms used to explain the navigation of birds in geomagnetic fields. However, little research has been done to explore the role of quantum entanglement in this mechanism. In this paper, we study the lifetime of radical pair entanglement corresponding to the magnitude and direction of magnetic fields to show that the entanglement lasts long enough in birds to be used for navigation. We also demonstrate that, due to a lack of orientational sensitivity of the entanglement in the geomagnetic field, the birds are not able to orient themselves b…
The radical-pair-based chemical reaction could be used by birds for the navigation via the geomagnetic direction. An inherent physical mechanism is that the quantum coherent transition from a singlet state to triplet states of the radical pair could response to the weak magnetic field and be sensitive to the direction of such a field and then results in different photopigments in the avian eyes to be sensed. Here, we propose a quantum bionic setup for the ultra-sensitive probe of a weak magnetic field based on the quantum phase transition of the environments of the two electrons in the radical…
We investigate the geometry of the four qubit systems by means of algebraic geometry and invariant theory, which allows us to interpret certain entangled states as algebraic varieties. More precisely we describe the nullcone, i.e., the set of states annihilated by all invariant polynomials, and also the so called third secant variety, which can be interpreted as the generalization of GHZ-states for more than three qubits. All our geometric descriptions go along with algorithms which allow us to identify any given state in the nullcone or in the third secant variety as a point of one of the 47 …
The quantum phase transition (QPT) of the one-dimensional (1D) quantum compass model in a transverse magnetic field is studied in this paper. An exact solution is obtained by using an extended Jordan and Wigner transformation to the pseudo-spin operators. The fidelity susceptibility, the concurrence, the block-block entanglement entropy, and the pseudo-spin correlation functions are calculated with antiperiodic boundary conditions. The QPT driven by the transverse field only emerges at zero field and is of the second-order. Several critical exponents obtained by finite size scaling analysis ar…
The matrix product state (MPS) is utilized to study the ground state properties and quantum phase transitions (QPTs) of the one-dimensional quantum compass model (QCM). The MPS wavefunctions are argued to be very efficient descriptions of QCM ground states, and are numerically determined by imaginary time projections. The ground state energy, correlations, quantum entanglement and its spectrum, local and nonlocal order parameters, etc., are calculated and studied in details. It is revealed that the bipartite and block entanglement entropies, as well as the nearest neighbor correlation function…
We study the correlations in the one-dimensional extended quantum compass model in a transverse magnetic field. By exactly solving the Hamiltonian, we find that the quantum correlation of the ground state of one-dimensional quantum compass model is vanishing. We show that quantum discord can not only locate the quantum critical points, but also discern the orders of phase transitions. Furthermore, entanglement quantified by concurrence is also compared.
Several experiments over the years have shown that the Earth's magnetic field is essential for orientation in birds migration. The most promising explanation for this orientation is the photo-stimulated radical pair (RP) mechanism. In order to define a reference frame for the orientation task radicals must have an intrinsic anisotropy. We show that this kind of anisotropy, and consequently the entanglement in the model, are not necessary for the proper functioning of the compass. Classically correlated initial conditions for the RP, subjected to a fast decoherence process, are able to provide …
We introduce a generalized two-dimensional orbital compass model, which interpolates continuously from the classical Ising model to the orbital compass model with frustrated quantum interactions, and investigate it using the multiscale entanglement renormalization ansatz (MERA). The results demonstrate that increasing frustration of exchange interactions triggers a second order quantum phase transition to a degenerate symmetry broken state which minimizes one of the interactions in the orbital compass model. Using boson expansion within the spin-wave theory we unravel the physical mechanism of…
Magnetic measurement can be performed by various sensors, such as SQUID and Giant Magnetoresistance. This device can achieve high accuracy while losing efficiency and convenience. The model of biological magnetic sensing in avian proposes a radical pair response to the external field on the FLY results in regulating animal behaviour. Inspired by the radical pair system found in biological system, the effect of intra-radical coupling and the initial condition is studied in this simplified radical pair model as the quantum advantage results from entanglement and superposition are investigated in…
Chemical magnetometers are radical pair systems such as solutions of pyrene and N,N-dimethylaniline (Py-DMA) that show magnetic field effects in their spin dynamics and their fluorescence. We investigate the existence and decay of quantum entanglement in free geminate Py-DMA radical pairs and discuss how entanglement can be assessed in these systems. We provide an entanglement witness and propose possible observables for experimentally estimating entanglement in radical pair systems with isotropic hyperfine couplings. As an application, we analyze how the field dependence of the entanglement l…
The radical-pair mechanism was introduced in the 1960's to explain anomalously large EPR and NMR signals in chemical reactions of organic molecules. It has evolved to the cornerstone of spin chemistry, the study of the effect electron and nuclear spins have on chemical reactions, with the avian magnetic compass mechanism and the photosynthetic reaction center dynamics being prominent biophysical manifestations of such effects. In recent years the radical-pair mechanism was shown to be an ideal biological system where the conceptual tools of quantum information science can be fruitfully applied…
What is the real role of the quantum coherence and entanglement in the radical pair (RP) compass, and what determines the singlet yield have not been fully understood. In this paper, we find that the dark states of the two-electron Zeeman energy operator (TEZE) play an important role in the RP compass. We respectively calculate the singlet yields for two initial states in this dark state basis: the coherent state and the same state just removing the dark state coherence. For the later there is neither dark state coherence nor entanglement in the whole dynamical process. Surprisingly we find th…
The yield of chemical reactions involving intermediate radical pairs is influenced by magnetic fields well beyond the levels expected from energy considerations. This dependence can be traced back to the microscopic dynamics of electron spins and constitutes the basis of the chemical compass. Here we propose a new experimental approach based on molecular photoswitches to achieve additional control on the chemical reaction and to allow short-time resolution of the spin dynamics. Our proposal enables experiments to test some of the standard assumptions of the radical pair model and improves the …
The mechanism used by migratory birds to orientate themselves using the geomagnetic field is still a mystery in many species. The radical pair mechanism, in which very weak magnetic fields can influence certain types of spin-dependent chemical reactions, leading to biologically observable signals, has recently imposed itself as one of the most promising candidates for certain species. This is thanks both to its extreme sensitivity and its capacity to reproduce results from behavioral studies. Still, in order to gain a directional sensitivity, an anisotropic mechanism is needed. Recent proposal…
Ever since the appearance of the seminal work of Einstein, Podolsky and Rosen (The EPR-paradox), the phenomenon of entanglement, which features the essential difference between classical and quantum physics, has received wide theoretical and experimental attentions. Recently the desire to understand and create quantum entanglement between particles such as spins, photons, atoms and molecules is fueled by the development of quantum teleportation, quantum communication, quantum cryptography and quantum computation. Although most of the work has focused on showing that entanglement violates the f…
Antiferromagnetic spin rings represent prototypical realizations of highly correlated, low-dimensional systems. Here we theoretically show how the introduction of magnetic defects by controlled chemical substitutions results in a strong spatial modulation of spin-pair entanglement within each ring. Entanglement between local degrees of freedom (individual spins) and collective ones (total ring spins) are shown to coexist in exchange-coupled ring dimers, as can be deduced from general symmetry arguments. We verify the persistence of these features at finite temperatures, and discuss them in ter…
We investigate the behavior of entanglement entropy at finite temperature and chemical potential for strongly coupled large-N gauge theories in $d$-dimensions ($d\ge 3$) that are dual to Anti-de Sitter-Reissner-Nordstrom geometries in $(d+1)-$dimensions, in the context of gauge-gravity duality. We develop systematic expansions based on the Ryu-Takayanagi prescription that enable us to derive analytic expressions for entanglement entropy and mutual information in different regimes of interest. Consequently, we identify the specific regions of the bulk geometry that contribute most significantly…
We theoretically investigate the quantum correlations (in terms of concurrence of indistinguishable electrons) in a prototype molecular system (hydrogen molecule). With the assistance of the standard approximations of the linear combination of atomic orbitals and the configuration interaction methods we describe the electronic wavefunction of the ground state of the H2 molecule. Moreover, we managed to find a rather simple analytic expression for the concurrence (the most used measure of quantum entanglement) of the two electrons when the molecule is in its lowest energy. We have found that co…
Recently, Yu, Brown, and Chuang [Phys. Rev. A {\bf 71}, 032341 (2005)] investigated the entanglement attainable from unitary transformed thermal states in liquid-state nuclear magnetic resonance (NMR). Their research gave an insight into the role of the entanglement in a liquid-state NMR quantum computer. Moreover, they attempted to reveal the role of mixed-state entanglement in quantum computing. However, they assumed that the Zeeman energy of each nuclear spin which corresponds to a qubit takes a common value for all; there is no chemical shift. In this paper, we research a model with the ch…
The spin dynamics of the diamond NV$^{-}$ center turns out to be similar to that of the chemical compass responsible for avian magnetoreception. We present a simulation framework based on quantum master equation for the former that is based upon the Radical Pair model of the latter. We show that this framework captures all the experimentally studied behavior of the NV$^{-}$ center spin system and can therefore be a predictive modeling tool.
Some chemical reactions are described by electron transfer (ET) processes. The underlying mechanism could be modeled as a polaron motion in the molecular crystal-the Holstein model. By taking spin degrees of freedom into consideration, we generalize the Holstein model (molecular crystal model) to microscopically describe an ET chemical reaction. In our model, the electron spins in the radical pair simultaneously interact with a magnetic field and their nuclear-spin environments. By virtue of the perturbation approach, we obtain the chemical reaction rates for different initial states. It is di…
We construct and analytically compute entanglement and the Rényi entropies of Dirac fermions on a 2 dimensional torus in the presence of background chemical potential, current source and Wilson loop, by employing correlation functions of the electromagnetic vertex operators of $\mathbb{Z}_n$ orbifold theory. The entropies reveal numerous novelties. They probe the energy levels of compact fermions through the chemical potential, demonstrate interference phenomena with the current source being `beat frequency,' and experience topological phase transitions by dialing the Wilson loop, in the low t…
We investigate the leading area-law contribution to entanglement entropy in a system described by a general Lagrangian with O(2) symmetry containing first- and second-order time derivatives, namely breaking the Lorentz-invariance. We establish a connection between the Higgs gap present in a symmetry-broken phase and the area-law term for the entanglement entropy in the general, non-relativistic case. Our predictions for the entanglement entropy and correlation length are successfully compared to numerical results in two paradigmatic systems: the Mott insulator to superfluid transition for ultr…
Chemical bonding concepts emerge naturally from maximally entangled atomic orbitals
Ludwig-Maximilians-Universität München（慕尼黑大学）；Munich Center for Quantum Science and Technology (MCQST)（慕尼黑量子科学与技术中心）；Donostia International Physics Center (DIPC)（圣塞巴斯蒂安国际物理中心）
A quantum framework, according quantum theories of electromagnetic (EM)radiation to matter response, leads to a handy scheme addressed to examine both physical and chemical processes. Fundamental quantum effects such asentanglement, coherence, de-coherence and re-coherence yield a fully quantum physical presentation applicable to chemical processes. A photonic basis-set obtains including all possibilities accessible to a system in abstract space; electronuclear (EN) base states put in resonance by photon fields are the ground where quantum states, q-states, would show time evolution. At labora…
We study the steady state entanglement and correlations of an open system comprised of two coupled fermions in the equilibrium or nonequilibrium environments and distill the nonequilibrium contribution to the quantum correlations. We show that in the equilibrium condition, the steady-state quantum correlations exhibit non-monotonic behavior, while in the nonequilibrium case, the monotonicity is determined by many parameters. The entanglement vanishes abruptly upon the increase of the temperature (bias) and chemical potential bias, it witnesses a critical chemical potential above which the conc…
A recent development in quantum chemistry has established the quantum mutual information between orbitals as a major descriptor of electronic structure. This has already facilitated remarkable improvements of numerical methods and may lead to a more comprehensive foundation for chemical bonding theory. Building on this promising development, our work provides a refined discussion of quantum information theoretical concepts by introducing the physical correlation and its separation into classical and quantum parts as distinctive quantifiers of electronic structure. In particular, we succeed in …
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 th…
The radical pair reaction underlies the magnetic field sensitivity of chemical reactions and is suggested to play an important role in both chemistry and biology. Current experimental evidence is based on ensemble measurements, however, the ability to probe the radical pair reaction at the single molecule level would provide valuable information concerning its role in important biological processes. Here, we propose a scheme to detect the charge recombination rate in a radical pair reaction under ambient conditions by using single nitrogen-vacancy center spin in diamond. We demonstrate theoret…
The accurate calculation of the (differential) correlation energy is central to the quantum chemical description of bond-formation and bond-dissociation processes. In order to estimate the quality of single- and multi-reference approaches for this purpose, various diagnostic tools have been developed. In this work, we elaborate on our previous observation [J. Phys. Chem. Lett. 3, 3129 (2012)] that one- and two-orbital-based entanglement measures provide quantitative means for the assessment and classification of electron correlation effects among molecular orbitals. The dissociation behavior o…
A quantum Matter-Photonics framework is adapted to help scrutinize chemical reaction mechanisms and used to explore a process mapped from chemical tree topological model. The chemical concept of bond knitting/breaking is reformulated via partitioned base sets leading to an abstract and general quantum presentation. Pivotal roles are assigned to entanglement, coherence,de-coherence and Feshbach resonance quantum states that permit apprehend gating states in conversion processes. A view from above in the state energy eigenvalue ladder, belonging to full system spectra complement the standard vie…
We theoretically investigate the hyperfine-induced decoherence in a pair of spin-cluster qubits, consisting of two exchange-coupled heterometallic wheels. We identify two distinct regimes in the decoherence of intermolecular entanglement and show that this can be substantially recovered through dynamical decoupling. Different chemical elements and physical processes are responsible for the decoherence of the singlet-triplet superposition, resulting in a wider tunability of its decoherence time.
We demonstrate that local transformations on a composite quantum system can be enhanced in the presence of certain entangled states. These extra states act much like catalysts in a chemical reaction: they allow otherwise impossible local transformations to be realised, without being consumed in any way. In particular, we show that this effect can considerably improve the efficiency of entanglement concentration procedures for finite states.
Electron correlation effects are essential for an accurate ab initio description of molecules. A quantitative a priori knowledge of the single- or multi-reference nature of electronic structures as well as of the dominant contributions to the correlation energy can facilitate the decision regarding the optimum quantum chemical method of choice. We propose concepts from quantum information theory as orbital entanglement measures that allow us to evaluate the single- and multi-reference character of any molecular structure in a given orbital basis set. By studying these measures we can detect po…
The random magnetic field produced by nuclear spins has long been viewed as the dominating source of decoherence in the quantum-dot based spins. Here we obtain in both exact and analytical manner the dynamics of spin qubits coupled to nuclear spin environments via the hyperfine interaction, going beyond the weak system-bath interaction and Markovian approximation. We predict that the detailed-balance breaking produced by chemical potential gradient in nuclear baths leads to the rapid oscillations of populations, quantum coherence and entanglement, which are absent in the conventional case (i.e…
Collectively coupling molecular ensembles to a cavity has been demonstrated to modify chemical reactions akin to catalysis. Theoretically understanding this experimental finding remains to be an important challenge. In particular the role of quantum effects in such setups is an open question of fundamental and practical interest. Theoretical descriptions often neglect quantum entanglement between nuclear and electro-photonic degrees of freedom, e.g.~by computing Ehrenfest dynamics. Here we discover that disorder can strongly enhance the build-up of this entanglement on short timescales after i…
Quantum correlations in molecules: from quantum resourcing to chemical bonding
Ludwig-Maximilians-Universität München（慕尼黑大学）；Munich Center for Quantum Science and Technology (MCQST)（慕尼黑量子科学与技术中心）；Algorithmiq Ltd.（算法有限公司）；ETH Zürich（苏黎世联邦理工学院）；Wigner Research Centre for Physics（维格纳物理研究中心）；Eötvös Loránd University（厄特沃什·罗兰大学）
We consider the quantum entanglement of the electronic and vibrational degrees of freedom in molecules with a tendency towards double welled potentials using model coupled harmonic diabatic potential-energy surfaces. The von Neumann entropy of the reduced density matrix is used to quantify the electron-vibration entanglement for the lowest two vibronic wavefunctions in such a bipartite system. Significant entanglement is found only in the region in which the ground vibronic state contains a density profile that is bimodal (i.e., contains two separate local minima). However, in this region two …
Femtosecond torsional relaxation processes experimentally detected and recently reported by Clark et al. (Nature Phys. 8,225 (2012)) are theoretically dissected with a Hilbert/Fock quantum physical (QP) framework incorporating entanglement of photon/matter base states overcoming standard semi-classic vibrational descriptions. The quantum analysis of a generic Z/E (cis/trans) isomerization in abstract QP terms shed light to fundamental roles played by photonic spin and excited electronic singlet coupled to triplet states. It is shown that one photon activation cannot elicit femtosecond phenomen…
Quantum computers are promising for simulations of chemical and physical systems, but the limited capabilities of today's quantum processors permit only small, and often approximate, simulations. Here we present a method, classical entanglement forging, that harnesses classical resources to capture quantum correlations and double the size of the system that can be simulated on quantum hardware. Shifting some of the computation to classical post-processing allows us to represent ten spin-orbitals on five qubits of an IBM Quantum processor to compute the ground state energy of the water molecule…
