M. Odelius et al., MOLECULAR-DYNAMICS SIMULATION OF THE ZERO-FIELD SPLITTING FLUCTUATIONS IN AQUEOUS NI(II), The Journal of chemical physics, 103(5), 1995, pp. 1800-1811
The fluctuations in the zero-held splitting (ZFS) of the electronic gr
ound state of the Ni(II) ion in aqueous solution have been studied thr
ough a combination of ab initio quantum chemistry calculations, includ
ing spin-orbit coupling, and molecular dynamics (MD) simulations. The
ab initio calculations for the hexa-aquo Ni(II) complex have been used
to generate an expression for the ZFS as a function of the distortion
s of the idealized T-h symmetry of the complex along the normal modes
of E(g) and T-2g symmetries. The MD simulations provide a 200 ps traje
ctory of motions in the system consisting of a Ni(II) ion and 255 wate
r molecules, which is analyzed in detail in terms of both the structur
e and the dynamics in the solvation sphere around the ion. The time co
rrelation function (TCF) for the ZFS interaction has been computed and
analyzed. It is found that the mean square amplitude of the ZFS is ab
out 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 subpicoseco
nd time scale, which is much faster than earlier proposals. It is also
interesting to note, for comparison with theoretical models, that the
ZFS tenser is far from cylindrical and that the normal modes of E(g)
och T-2g symmetry both contribute to its fluctuations. (C) 1995 Americ
an Institute of Physics.