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http://hdl.handle.net/20.500.12188/1629
Title: | Different structures give similar vibrational spectra: the case of OH- in aqueous solution | Authors: | Mitev, Pavlin D Bopp, Philippe A Petreska, Jasmina Coutinho, Kaline Ågren, Hans Pejov, Ljupco Hermansson, Kersti |
Issue Date: | 14-Feb-2013 | Publisher: | AIP Publishing | Journal: | The Journal of chemical physics | Abstract: | We have calculated the anharmonic OH(-)(aq) vibrational spectrum in aqueous solution with a "classical Monte Carlo simulation + QM/MM + vibrational" sequential approach. A new interaction model was used in the Monte Carlo simulations: a modified version of the charged-ring hydroxide-water model from the literature. This spectrum is compared with experiment and with a spectrum based on CPMD-generated structures, and the hydration structures and H-bonding for the two models are compared. We find that: (i) the solvent-induced frequency shift as well as the absolute OH(-) frequency are in good agreement with experiment using the two models; (ii) the Raman and IR bands are very similar, in agreement with experiment; (iii) the hydration structure and H-bonding around the ion are very different with the two ion-water interaction models (charged-ring and CPMD); (iv) a cancellation effect between different regions of the hydration shell makes the total spectra similar for the two interaction models, although their hydration structures are different; (v) the net OH(-) frequency shift is a blueshift of about +80 cm(-1) with respect to frequency of the gas-phase ion. | URI: | http://hdl.handle.net/20.500.12188/1629 | DOI: | 10.1063/1.4775589 |
Appears in Collections: | Faculty of Natural Sciences and Mathematics: Journal Articles |
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