Quantitative Structure-Based Prediction of Electron Spin Decoherence in Organic Radicals

The decoherence, or dephasing, of electron spins in paramagnetic molecules limits sensitivity and resolution in electron paramagnetic resonance spectroscopy, and it represents a challenge for utilizing paramagnetic molecules as qubit units in quantum information devices. For organic radicals in dilute frozen aqueous solution at cryogenic temperatures, electron spin decoherence is driven by neighboring nuclear spins. Here, we show that this nuclear-spin-driven decoherence can be quantitatively predicted from the molecular structure and solvation geometry of the radicals. We use a fully deterministic quantum model of the electron spin and up to 2000 neighboring protons with a static spin Hamiltonian that includes nucleus-nucleus couplings. We present experiments and simulations of two nitroxide radicals and one trityl radical, which have decoherence time scales of 4-5 μs below 60 K. We show that nuclei within 12 Å of the electron spin contribute to decoherence, with the strongest impact from protons 4-8 Å away.