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arXiv:2603.14677

Stochastic Collision Theory of Magnetism in Radical Fluids

Yoshiaki Uchida, Ryohei Kishi

physics.chem-phcond-mat.mtrl-scicond-mat.stat-mechquant-phSubmitted Mar 16, 2026• Announced Mar 17, 2026• Revised May 23, 2026 (v2)
v1 · Mar 16, 2026v2 · May 23, 2026
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Abstract

How stochastic, microscopic events generate deterministic, macroscopic properties is a fundamental question in physics. We address this question by developing a quantum master equation model for concentrated radical solutions, where random molecular collisions govern the magnetic properties of the system. Our theory reveals a simple mechanism: the first-order exchange contribution averages to zero over collisions, while the second-order term survives as an effective ferromagnetic coupling that enhances magnetization. The model captures the experimentally observed trends in magnetic behavior that deviate from conventional theories. Because the mechanism arises from statistical averaging, it may apply to a broader class of soft matter phenomena, including liquid crystals.

Comments
5 pages, 4 figures

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How stochastic, microscopic events generate deterministic, macroscopic properties is a fundamental question in physics. We address this question by developing a quantum master equation model for concentrated radical solutions, where random molecular collisions govern the magnetic properties of the system. Our theory reveals a simple mechanism: the first-order exchange contribution averages to zero over collisions, while the second-order term survives as an effective ferromagnetic coupling that enhances magnetization. The model captures the experimentally observed trends in magnetic behavior that deviate from conventional theories. Because the mechanism arises from statistical averaging, it may apply to a broader class of soft matter phenomena, including liquid crystals.
It is a remarkable fact that the interactions between electron and nuclear spins, and their interactions with a magnetic field, can have a profound effect on chemical reactivity, despite the fact that the characteristic interaction energies are orders of magnitude smaller than thermal energy. These observations are explained by the existence of long-lived quantum coherences between spins in certain molecular species (in particular radical pairs), and the study of these spin effects constitutes the field of spin chemistry, a field which spans a wide range of systems, from biochemical reactions to device physics. Because spin chemistry involves subtle quantum effects, many intuitive models used by Physical Chemists, in particular classical kinetic equations, cannot be universally applied. On the other hand, complete first principles modelling of reactions involving spin effects comes at an impossibly high computational cost in complex systems, and often offers little physical insight. In order to address the shortcomings of these approaches, quantum master equations (QMEs) are employed to describe spin chemical phenomena. These are equations that describe a reduced set of degrees of freedom quantum mechanically, accounting for the effects of remaining degrees freedom implicitly. In this thesis I explore the use of QME techniques to resolve a range of problems in spin chemistry. These techniques can be used to obtain the correct radical pair spin QME, resolving questions about the role of quantum measurement in these systems. As well as aiding the development of the theory of spin chemistry, QMEs provide a practical tool for modelling radical pair reactions including spin relaxation effects, as I also demonstrate. As a final study of QME techniques in spin chemistry, I use these methods to show when the classical kinetic description of radical pair reactions is and is not valid.
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In terms of the stochastic process of quantum-mechanical version of Markov chain Monte Carlo method (the MCMC), we analytically derive macroscopically deterministic flow equations of order parameters such as spontaneous magnetization in infinite-range ( d (= ∞ )-dimensional) quantum spin systems. By means of the Trotter decomposition, we consider the transition probability of Glauber-type dynamics of microscopic states for the corresponding ( d + 1)-dimensional classical system. Under the static approximation, differential equations with respect to macroscopic order parameters are explicitly obtained from the master equation that describes the microscopic-law. In the steady state, we show that the equations are identical to the saddle point equations for the equilibrium state of the same system. The equation for the dynamical Ising model is recovered in the classical limit. We also check the validity of the static approximation by making use of computer simulations for finite size systems and discuss several possible extensions of our approach to disordered spin systems for statistical-mechanical informatics. Especially, we shall use our procedure to evaluate the decoding process of Bayesian image restoration. With the assistance of the concept of dynamical replica theory (the DRT), we derive the zero-temperature flow equation of image restoration measure showing some 'non-monotonic' behaviour in its time evolution.
The development of the radical pair mechanism has allowed for theoretical explanation of the fact that magnetic fields are observed to have an effect on chemical reactions. The mechanism describes how an external magnetic field can alter chemical yields by interacting with the spin state of a pair of radicals. In the field of quantum biology, there has been some interest in the application of the mechanism to biological systems. This paper takes an open quantum systems approach to a model of the radical pair mechanism in order to derive a master equation in the Born-Markov approximation for the case of two electrons, each interacting with an environment of nuclear spins as well as the external magnetic field, then placed in a dissipative bosonic bath. This model is used to investigate two different cases relating to radical pair dynamics. The first uses a collective coupling approach to simplify calculations for larger numbers of nuclei interacting with the radical pair. The second looks at the effects of different hyperfine configurations of the radical pair model, for instance the case in which one of the electrons interact with two nuclei with different hyperfine coupling constants. The results of these investigations are analysed to see if they offer any insights into the biological application of the radical pair mechanism in avian magnetoreception.
We introduce the stochastic Boltzmann equation (SBE) as an approach for exploring the spin dynamics of magnetic molecules coupled to a stochastic environment. The SBE is a time-evolution equation for the probability density of the spin density matrix of the system. This probability density is relevant to experiments which take measurements on single molecules, in which probabilities of observing particular spin states (rather than ensemble averages) are of interest. By analogy with standard treatments of the regular Boltzmann equation, we propose a relaxation-time approximation for the SBE and show that solutions to the SBE under the relaxation-time approximation can be obtained by performing simple trajectory simulations for the case of a boson gas environment. Cases where the relaxation-time approximation are satisfied can therefore be investigated by careful choice of the parameters for the boson gas environment, even if the actual environment is quite different from a boson gas. The application of the SBE approach is demonstrated through an illustrative example.