The fluctuations in the zero‐field splitting (ZFS) of the electronic ground state of the Ni(II) ion in aqueous solution have been studied through a combination of abinitio quantum chemistry calculations, including spin–orbit coupling, and molecular dynamics (MD) simulations. The abinitio calculations for the hexa‐aquo Ni(II) complex have been used to generate an expression for the ZFS as a function of the distortions of the idealized Th symmetry of the complex along the normal modes of Eg and T2g symmetries. The MD simulations provide a 200 ps trajectory of motions in the system consisting of a Ni(II) ion and 255 water molecules, which is analyzed in detail in terms of both the structure and the dynamics in the solvation sphere around the ion. The time correlation function (TCF) for the ZFS interaction has been computed and analyzed. It is found that the mean square amplitude of the ZFS is about 5.2 cm−1, which is about twice the estimates based on the model‐dependent analysis of the proton spin relaxation in the aqueous Ni(II) solution. The decay of the ZFS TCF is found to occur on a subpicosecond time scale, which is much faster than earlier proposals. It is also interesting to note, for comparison with theoretical models, that the ZFS tensor is far from cylindrical and that the normal modes of Eg och T2g symmetry both contribute to its fluctuations.

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