## Abstract

Photoelectron spectra (PESs) of Li^{-}(NH_{3})_{n} (n ≤ 16), Na^{-}(NH_{3})_{n} (n ≤ 12), and Na^{-}(H_{2}O)_{n} (n ≤ 7), as well as the ionization potentials (IPs) of Li(NH_{3})_{n} (n ≤ 28) and Li(H_{2}O)_{n} (n ≤ 46), are examined. PESs of Li^{-}(NH_{3})_{n} (n ≤ 10) exhibit three bands derived from the Li(3^{2}S)-Li^{-}(^{1}S), Li(2^{2}P)-Li^{-}(^{1}S), and Li(2^{2}S)-Li^{-}(^{1}S) transitions. The vertical detachment energies of the 3^{2}S- and 2^{2}P-type states decrease dramatically with increasing n. For n ≥ 11, the transitions to the 2^{2}P- and 3^{2}S-type states almost become degenerate with the transition of the neutral ground (2^{2}S) state. In addition to these observations, we also find the red shift of the 2^{2}S-type transition with a much slower rate. The similar spectral trends are also observed for the Na(3^{2}P)-Na^{-}(^{1}S) and Na(3^{2}S)-Na^{-}(^{1}S) transitions of Na^{-}(NH_{3})_{n}. On the other hand, the transitions of Na^{-}(H_{2}O)_{n} exhibit the opposite shifts, and the ^{2}P-^{2}S energy separation does not change. As for Li(H_{2}O)_{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(H_{2}O)_{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.

Original language | English |
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Pages (from-to) | 3078-3087 |

Number of pages | 10 |

Journal | Journal of Physical Chemistry A |

Volume | 101 |

Issue number | 17 |

DOIs | |

Publication status | Published - 1997 Apr 24 |

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