Structures and excitation energies of ozone-water clusters O3(H2O)n (n = 1-4) |
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| Authors: | Hiroto Tachikawa Shigeaki Abe |
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| Institution: | a Division of Molecular Chemistry, Graduate School of Chemistry, Hokkaido University, Sapporo 060-8628, Japan
b Bioscience division, Los Alamos National Laboratory, Los Alamos, NM 87545, USA |
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| Abstract: | Hybrid density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations have been carried out for ozone-water clusters O3(H2O)n (n = 1-4) in order to obtain hydration effects on the absorption spectrum of ozone. The first water molecule in n = 1 is bound to the ozone molecule by an oxygen orientation form in which the oxygen atom of H2O orients the central oxygen atom of O3. In n = 2, the water dimer is bound to O3 and then the cyclic structure is formed as the most stable structure. For n = 3 (or n = 4), the cyclic water trimer (or tetramer) is bound by a hydrogen bond to the ozone molecule. The TD-DFT calculations of O3(H2O)n (n = 0-4) show that the first and second excitation energies of O3 are blue-shifted by the interaction with the water clusters. The magnitude of the spectral shift is largest in n = 2, and the shifts of the excitation energies are +0.07 eV for S1 and +0.13 eV for S2 states. In addition to the spectral shifts (S1 and S2 states), it is suggested that a charge-transfer band is appeared as a low-lying excited state above the S1 and S2 states. The origin of the spectrum shifts was discussed on the basis of theoretical results. |
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| Keywords: | Ozone-water complex Excitation energy Hydration structure Spectral shift |
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