The
physicochemical properties of the three heaviest alkaline-earth
cations, Sr
2+
, Ba
2+
, and Ra
2+
in
water have been studied by means of classical molecular dynamics (MD)
simulations. A specific set of cation–water intermolecular
potentials based on ab initio potential energy surfaces has been built
on the basis of the hydrated ion concept. The polarizable and flexible
model of water MCDHO2 was adopted. The theoretical–experimental
comparison of structural, dynamical, energetic, and spectroscopical
properties of Sr
2+
and Ba
2+
aqueous solutions
is satisfactory, which supports the methodology developed. This good
behavior allows a reasonable reliability for the predicted Ra
2+
physicochemical data not experimentally determined yet.
Simulated extended X-ray absorption fine-structure (EXAFS) and X-ray
absorption near-edge spectroscopy spectra have been computed from
the snapshots of the MD simulations and compared with the experimental
information available for Sr
2+
and Ba
2+
. For
the Ra
2+
case, the Ra L
3
-edge EXAFS spectrum
is proposed. Structural and dynamical properties of the aqua ions
for the three cations have been obtained and analyzed. Along the [M(H
2
O)
n
]
m
+
series, the M–O distance for the first-hydration shell is
2.57, 2.81, and 2.93 Å for Sr
2+
, Ba
2+
,
and Ra
2+
, respectively. The hydration number also increases
when one is going down along the group: 8.1, 9.4, and 9.8 for Sr
2+
, Ba
2+
, and Ra
2+
, respectively. Whereas
[Sr(H
2
O)
8
]
2+
is a typical aqua ion
with a well-defined structure, the Ba
2+
and Ra
2+
hydration provides a picture exhibiting an average between the ennea-
and the deca-hydration. These results show a similar chemical behavior
of Ba
2+
and Ra
2+
aqueous solutions and support
experimental studies on the removal of Ra-226 of aquifers by different
techniques, where Ra
2+
is replaced by Ba
2+
.
A comparison of the heavy alkaline ions, Rb
+
and Cs
+
, with the heavy alkaline-earth ions is made.