TY - JOUR
T1 - Microscopic solvation process of alkali atoms in finite clusters
T2 - Photoelectron and photoionization studies of M(NH3)n and M(H2O)n (M = Li, Li-, Na-)
AU - Takasu, Ryozo
AU - Misaizu, Fuminori
AU - Hashimoto, Kenro
AU - Fuke, Kiyokazu
PY - 1997/4/24
Y1 - 1997/4/24
N2 - 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.
AB - 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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U2 - 10.1021/jp9629654
DO - 10.1021/jp9629654
M3 - Article
AN - SCOPUS:0000007069
VL - 101
SP - 3078
EP - 3087
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 17
ER -