Web Release Date: October 4,
Ab Initio Molecular Dynamics Simulations of an Excited State of X-(H2O)3 (X = Cl, I) Complex
aski,
and
National Creative Research Initiative Center for Superfunctional Materials and Department of Chemistry, Division of Molecular and Life Sciences, Pohang University of Science and Technology, San 31, Hyojadong, Namgu, Pohang, 790-784, Korea, and Molecular Interactions and Transformations, Chemical Sciences Division, Pacific Northwest National Laboratory, K1-83, P.O. Box 999, 906 Battelle Boulevard, Richland, WA 99352
Received: March 11, 2005
In Final Form: August 24, 2005
Abstract:
Upon excitation of Cl-(H2O)3 and I-(H2O)3 clusters, the electron transfers from the anionic precursor to the solvent, and then the excess electron is stabilized by polar solvent molecules. This process has been investigated using ab initio molecular dynamics (AIMD) simulations of excited states of Cl-(H2O)3 and I-(H2O)3 clusters. The AIMD simulation results of Cl-(H2O)3 and I-(H2O)3 are compared, and they are found to be similar. Because the role of the halogen atom in the photoexcitation mechanism is controversial, we also carried out AIMD simulations for the ground-state bare excess electron-water trimer [e-(H2O)3] at 300 K, the results of which are similar to those for the excited state of X-(H2O)3 with zero kinetic energy at the initial excitation. This indicates that the rearrangement of the complex is closely related to that of e-(H2O)3, whereas the role of the halide anion is not as important.
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