Aqueous Solvation Free Energies of Ions and Ion Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton
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1 Supporting Information for: Aqueous Solvation Free Energies of Ions and Ion Water Clusters Based on an Accurate Value for the Absolute Aqueous Solvation Free Energy of the Proton Casey P. Kelly, Christopher J. Cramer, Donald G. Truhlar Department of Chemistry and Supercomputing Institute, 207 Pleasant St. SE, University of Minnesota, Minneapolis, MN journal: J. Phys. Chem. B date of preparation: July 10, 2006 number of pages: 15 Tables S1-S6. Slopes, Intercepts, and Y i Values (kcal/mol), Computed Using Various Data Sets 2 Table S7. y ij values (kcal/mol) Computed Using Various Data Sets.. 5 Cartesian Coordinates of the Ion-Water Clusters Used to Test the Continuum Models 6 1
2 TABLE S1: Slopes, Intercepts, and Y Values (kcal/mol), Computed Using All of the Conventional Aqueous Solvation Free Eneriges in Table 5 n slope intercept Y a average a Y is the average intersection ordinate of the nth straight line with all the others in this table. TABLE S2: Slopes, Intercepts, and Y Values (kcal/mol), Computed Using the Monatomic Cation Subset n slope intercept Y a average a Y is the average intersection ordinate of the nth straight line with all the others in this table. 2
3 TABLE S3: Slopes, Intercepts, and Y Values (kcal/mol), Computed Using the Oxonium Ion Subset n slope intercept Y a average a Y is the average intersection ordinate of the nth straight line with all the others in this table. TABLE S4: Slopes, Intercepts, and Y Values (kcal/mol), Computed Using the Ammonium Ion Data Set n slope intercept Y a average a Y is the average intersection ordinate of the nth straight line with all the others in this table. 3
4 TABLE S5: Slopes, Intercepts, and Y Values (kcal/mol), Computed Using Experimental Gas-Phase Clustering Free Energies Only n slope intercept Y a average a Y is the average intersection ordinate of the nth straight line with all the others in this table. TABLE S6: Slopes, Intercepts, and Y Values (kcal/mol), Computed Using the Conventional Aqueous Solvation Free Eneriges and Gas-Phase Clustering Free Energies Reported by Tissandier et al. a n slope Intercept Y a average a Tissandier, M. D.; Cowen, K. A.; Feng, W. Y.; Gundlach, E.; Cohen, M. J.; Earhart, A. D.; Coe, J. V. J. Phys. Chem. A 1998, 102, b Y is the average intersection ordinate of the nth straight line with all the others in this table. 4
5 TABLE S7: y ij values (kcal/mol) Computed Using Experimental Clustering Free Energies, by Subset a i j all ions monatomic cations oxonium ions ammonium ions all ions (expt. clustering free energies only) Tissandier et al. Data s.d. d a y ij is the ordinate of the intersection between the ith and jth straight lines, where i and j refer to the number of clustering water molecules. 5
6 Cartesian coordinates of ion-water clusters used to test the continuum models. Bare ion listed first, followed by the name of the corresponding neutral species. H3O+ water CH3OH2+ methanol CH3CH2OH2+ ethanol
7 (CH3)2OH+ dimethyl ether (C2H5)2OH+ diethyl ether
8 CH3C(OH)CH3+ acetone CH3C(OH)C6H5+ acetophenone NH4+ ammonia
9 F- hydrofluoric acid Cl- hydrochloric acid Br- hydrobromic acid OH- water HO2- hydrogen peroxide
10 O2- hydroperoxyl radical HS- hydrogen sulfide C2H- acetylene CN- hydrogen cyanide CH3O- methanol
11 C2H5O- ethanol CH3CH2CH2O- 1-propanol (CH3)2CHO- 2-propanol
12 CH3CH2CHOCH3-2-butanol C(CH3)3O- t-butanol
13 H2C=CHCH2O- allyl alcohol CH3OCH2CH2O- 2-methoxyethanol HOCH2CH2O- 1,2-ethanediol
14 C6H5CH2O- benzyl alcohol CF3CH2O- 2,2,2-trifluoroethanol CH(CF3)2O- 1,1,1,3,3,3-hexafluoropropan-2-ol
15 CH3OO- methyl hydroperoxide CH3CH2OO- ethyl hydroperoxide END OF SUPPORTING INFORMATION 15
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Radiation Chemistry Ionizing radiation produces abundant secondary electrons that rapidly slow down (thermalize) to energies below 7.4 ev, the threshold to produce electronic transitions in liquid water.
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