With ab initio molecular orbital calculations, the structures of the cation clusters Mg+(H20)" and their hydrogen-eliminated products (Mg0H)+(H20)"-i are optimized. In Mg+(H20)", the hydration number of the most stable isomer is 3. In (Mg0H)+(H20)"-i, all water molecules are directly bonded to Mg+ for n < 6. The hydration energy of (MgOH)+ is larger than that of Mg+ because of the strongly polarized (MgOH)+ molecular ion; Mg is oxidized halfway to Mg(II). The internal energy change of the hydrogen elimination of Mg+(H20)" is positive for n = 1-5, but becomes negative for n = 6, which is in good agreement with the product switching in the TOF spectrum reported in the preceding paper by Sanekata et al. The effects of isotope substitution and equilibrium constants of the hydrogen (deuterium) elimination reaction observed in their experiment can be explained qualitatively.
Photoelectron spectra (PESs) of
Li-(NH3)
n
(n ≤ 16),
Na-(NH3)
n
(n ≤ 12), and
Na-(H2O)
n
(n ≤ 7), as well
as the ionization potentials (IPs) of
Li(NH3)
n
(n ≤ 28)
and Li(H2O)
n
(n ≤
46), are examined. PESs of
Li-(NH3)
n
(n ≤ 10) exhibit three bands derived from the
Li(32S)−Li-(1S),
Li(22P)−Li-(1S), and
Li(22S)−Li-(1S)
transitions. The vertical detachment energies of the
32S- and 22P-type states decrease dramatically
with
increasing n. For n ≥ 11, the transitions
to the 22P- and 32S-type states almost become
degenerate with the
transition of the neutral ground (22S) state. In
addition to these observations, we also find the red shift of
the
22S-type transition with a much slower rate. The
similar spectral trends are also observed for the
Na(32P)−Na-(1S) and
Na(32S)−Na-(1S)
transitions of
Na-(NH3)
n
.
On the other hand, the transitions of
Na-(H2O)
n
exhibit the opposite shifts, and the 2P−2S
energy separation does not change. As for
Li(H2O)
n
, we find
a
monotonous decrease in IPs with n ≤ 4 and a constant IP
behavior for n ≥ 5. The limiting value for
n →
∞ (3.12 eV) is comparable to the estimated photoelectric threshold of
ice as in the case of Cs(H2O)
n
reported
previously. On the basis of these results as well as those of the
ab initio calculations, we discuss the early
stage of solvated-electron formation in finite clusters.
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