Electronic structure of the water dimer cation |
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Authors: | Pieniazek Piotr A VandeVondele Joost Jungwirth Pavel Krylov Anna I Bradforth Stephen E |
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Institution: | Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, USA. |
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Abstract: | The spectroscopic signatures of proton transfer in the water dimer cation were investigated. The six lowest electronic states were characterized along the reaction coordinate using the equation-of-motion coupled-cluster with single and double substitutions method for ionized systems. The nature of the dimer states was explained in terms of the monomer states using a qualitative molecular orbital framework. We found that proton transfer induces significant changes in the electronic spectrum, thus suggesting that time-resolved electronic femtosecond spectroscopy is an effective strategy to monitor the dynamics following ionization. The electronic spectra at vertical and proton-transferred configurations include both local excitations (features similar to those of the monomers) and charge-transfer bands. Ab initio calculations were used to test the performance of a self-interaction correction for density functional theory (DFT). The corrected DFT/BLYP method is capable of quantitatively reproducing the proper energetic ordering of the (H2O)2(+) isomers and thus is a reasonable approach for calculations of larger systems. |
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