Spin dynamics simulation of polarization transfer in spin-exchange optical pumping

Perttu Hilla, Rajgowrav Cheenikundil, Juha Vaara

Spin-exchange optical pumping (SEOP) is a method for producing spin-hyperpolarized noble gas nuclei, such as 129Xe and 131Xe, which are used in various magnetic resonance applications from fundamental physics to quantum sensing and medical imaging. In SEOP, optically polarized alkali-metal atoms transfer their spin polarization to the noble gas nuclei in gas-phase collision events via the hyperfine coupling (HFC) between the alkali valence electron and the noble gas nucleus. While the polarization transfer physics of spin $I = 1/2$ nuclei, such as 129Xe, is relatively well understood, that of spin $I > 1/2$ nuclei, such as 131Xe ($I = 3/2$), has been far less studied, and no rigorous theoretical model has been presented to date. To this end, we derive a simple analytical model for the upper limit, neglecting relaxation, of the SEOP polarization transfer, applicable to noble gases with arbitrary nuclear spin. Analytical evaluation of the Baker-Campbell-Hausdorff expansion for the time evolution of the spin density operator $\hatρ(t)$ reveals that only even-order terms in the HFC contribute to the polarization transfer, with the leading-order quadratic term being the most significant. We obtain a result similar to that derived for the spin-exchange cross section by Herman [Phys. Rev. 137, A 1062 (1965)], but in a more general framework for the time evolution of $\hatρ(t)$ that is also more familiar to magnetic resonance researchers. The model is applied to understand the difference in the polarization transfer efficiency between 129Xe and 131Xe, yielding results in agreement with previous experiments. We also validate the model by comparison to detailed numerical multiscale simulations of the SEOP process, where full quantum-chemically computed spin Hamiltonians sampled from molecular dynamics simulations of the gas-phase collision events are used to propagate the spin dynamics.

Ian A. Nelson

Bien Chann

Jyrki Rantaharju, Matti Hanni, Juha Vaara

Spin-exchange optical pumping (SEOP) enables hyperpolarization of magnetic noble gas nuclei and allows enormously enhanced signal in nuclear magnetic resonance studies in materials, biosciences, and medicine. We model the dynamics of the SEOP process taking place in a $\mathrm{Rb}\ensuremath{-}^{129}\mathrm{Xe}$ gas mixture and shed light on how the different microscopic processes influence the macroscopic polarization transfer. For each Rb-Xe collision taking place in simulated molecular dynamics trajectory, we sample a time series of quantum-chemically preparametrized Hamiltonians. Combined electron and nuclear spin dynamics of each event is propagated by solving the corresponding Liouville--von Neumann equation. The rarely occurring, long-lived van der Waals molecules are seen to give the most significant contribution to polarization transfer under the simulated conditions ($T=300$ K, $p=2.4$ bar), in agreement with earlier findings. Besides the lifetime of the collision complex, the average and minimum Rb-Xe interatomic distances characterize the efficiency of the polarization transfer events. We obtain insight into magnetization transfer in both individual binary collisions and van der Waals complexes and demonstrate a stepwise buildup of $^{129}\mathrm{Xe}$ spin polarization upon bond-length oscillations in the latter.

Earl Babcock, Ian A. Nelson, Steve Kadlececk +4 more

Thad G Walker, W. Happer

Spin-exchange optical pumping of mixtures of alkali-metal vapors and noble gases can be used to efficiently polarize the nuclei of the noble-gas atoms. Liters of noble gases at standard temperature and pressure and with nuclear spin polarizations of several tens of percent are now used in many applications. The authors describe the basic phenomena that govern the spin-exchange process and review the physics of angular momentum transfer and loss in optical pumping and spin-exchange collisions.