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Article

Photodissociation Spectroscopy of Li−H₂O and Li−D₂O Complexes

Supporting Info

Ryozo Takasu,^† Kaori Nishikawa,^† Nobuaki Miura,^‡ Akiyoshi Sabu,^‡ Kenro Hashimoto,^‡ Claus P. Schulz,^§ Ingolf V. Hertel,^§ and Kiyokazu Fuke*^†

Department of Chemistry, Kobe University, Nada-ku, Kobe 6578501 Japan, Computer Center and Department of Chemistry, Tokyo Metropolitan University, 1-1, Minami-Ohsawa, Hachioji-shi, Tokyo 192-0973 Japan/ACT-JST, and Max-Born-Institut, Rudower Chaussee 6, D-12489, Berlin, Germany

J. Phys. Chem. A, 2001, 105 (27), pp 6602–6608

DOI: 10.1021/jp004202t

Publication Date (Web): June 16, 2001

†

Kobe University.

‡

Tokyo Metropolitan University.

Max-Born-Institut.

Author to whom correspondence should be addressed. E-mail: fuke@kobe-u.ac.jp.

Abstract

The absorption spectra of Li−H₂O and Li−D₂O, produced by the laser vaporization technique, are examined in the energy region of 10300−11700 cm^-1 using a photodepletion method. Vibrationally resolved bands beginning at energies of 10464 and 10525 cm^-1 are observed for Li−H₂O and Li−D₂O, respectively. These peaks are assigned to the transition from the 1²A₁ ground state to the 2²A₁ excited state correlating to Li(²P) + H₂O(¹A₁). This transition is more than 4000 cm^-1 to the red of the Li (²P−²S) atomic transition. The extensive redshift of the 2²A₁−1²A₁ transition is ascribed to the large increase in ionic character in the upper state due to partial electron transfer. The spectrum of the Li−H₂O complex exhibits two extra vibronic bands in the region of 300−500 cm^-1 above the origin. These bands are tentatively ascribed to the transitions as a result of vibronic interaction between the low-lying excited states.