S1 Supporting Information (PART II) Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions Aleksandr V. Marenich, Christopher J. Cramer,* and Donald G. Truhlar* Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, MN 55455-0431 Prepared for the Journal of Physical Chemistry B Revised March 27, 2009 Number of pages: 10 * Corresponding author e-mail: cramer@umn.edu (C.J.C) and truhlar@umn.edu (D.G.T.)
S2 Contents: Table S1. Mean Signed Errors in Aqueous Solvation Free Energies, by Solute Class Table S2. Mean Signed Errors in Nonaqueous Solvation Free Energies, by Solute Class Table S3. Mean Signed Errors in Transfer Free Energies between Water and Organic Solvents, by Solute Class Table S4. Errors in Solvation and Transfer Free Energies for Neutrals, by Solvent page S3 S5 S7 S8
S3 Table S1. Mean Signed Errors (kcal/mol) in Aqueous Solvation Free Energies, by Solute Class a solute class N M05-2X B3LYP HF MIDI!6D 6-31G* 6-31+G** cc-pvtz 6-31G* 6-31G* H 2,NH 3,H 2 O,(H 2 O) 2 4 0.24 1.13 1.46 0.25 0.58 1.38 unbranched alkanes 8 0.04 0.11 0.26 0.32 0.07 0.04 branched alkanes 5 0.03 0.13 0.33 0.42 0.08 0.03 cycloalkanes 5 0.05 0.06 0.22 0.25 0.15 0.08 alkenes 9 0.04 0.22 0.51 0.43 0.20 0.12 alkynes 5 0.14 0.48 0.74 0.80 0.00 0.64 arenes 8 0.19 0.26 0.62 0.33 0.95 0.20 alcohols 12 0.97 0.12 0.91 0.11 0.59 0.77 phenols 4 0.28 0.48 0.95 0.05 0.86 0.87 ethers 12 0.71 0.20 0.76 0.05 0.99 0.34 aldehydes 6 1.31 0.02 1.20 0.81 0.83 1.77 ketones 12 1.28 0.16 1.32 0.96 0.52 1.79 carboxylic acids 5 1.97 0.55 0.25 0.34 1.32 1.06 esters 13 0.82 0.23 1.13 0.66 0.50 1.71 peroxides 3 0.03 1.26 1.78 0.74 0.55 1.98 bifunctional H,C,O compounds 5 1.20 0.12 1.11 0.10 0.96 1.43 aliphatic amines 15 0.72 0.10 0.77 0.13 0.61 0.02 anilines 7 0.11 0.38 0.84 0.14 0.94 0.24 aromatic N-heterocycles (1 N) 10 1.04 0.51 0.37 0.12 1.35 0.19 aromatic N-heterocycles (2 Ns) 3 0.56 0.53 1.86 1.17 0.29 1.83 nitriles 4 1.68 0.64 0.17 0.14 0.95 0.25 hydrazines 3 0.64 0.58 1.66 0.17 0.06 0.76 bifunctional H,C,N compounds 3 0.58 0.75 1.79 0.33 0.42 1.35 amides 4 3.08 1.36 0.15 0.88 2.42 0.14 ureas 2 2.48 0.86 0.22 0.73 2.25 0.26 nitrohydrocarbons 7 1.34 0.41 0.50 0.07 1.11 1.56 bifunctional H,C,N,O compounds 3 0.43 0.48 1.87 0.50 0.41 1.15
S4 Table S1. Continued solute class N M05-2X B3LYP HF MIDI!6D 6-31G* 6-31+G** cc-pvtz 6-31G* 6-31G* fluoroalkanes 5 0.55 0.29 0.39 0.07 0.52 0.25 fluoroarenes 1 0.20 0.19 0.85 0.43 0.67 0.46 chloroalkanes 13 0.64 0.52 0.86 0.52 0.32 0.84 chloroalkenes 6 0.25 0.42 0.19 0.46 0.68 0.10 chloroarenes 8 0.62 0.61 1.02 0.52 0.34 0.91 bromoalkanes 9 0.03 0.53 0.95 0.74 0.23 0.66 bromoalkenes 1 0.16 0.78 1.35 0.97 0.26 0.97 bromoarenes 4 0.18 0.58 1.05 0.69 0.27 0.68 multihalogen hydrocarbons 12 0.25 0.16 0.26 0.03 0.34 0.26 halogenated bifunctional compounds 9 1.63 0.61 0.41 0.44 1.28 0.68 thiols 4 0.38 0.21 0.53 0.09 0.22 0.15 sulfides 5 0.16 0.24 0.14 0.26 0.69 0.33 disulfides 2 0.00 0.11 0.26 0.21 0.52 0.09 sulfur heterocycles 1 0.04 0.01 0.26 0.04 0.66 0.22 halogenated sulfur compounds 2 0.22 0.21 0.71 0.06 0.41 1.32 phosphorus compounds 14 1.36 0.38 0.33 0.70 1.47 1.62 silicon compounds 1 0.90 0.71 0.45 0.42 1.04 0.75 all neutral data 274 0.57 0.05 0.71 0.16 0.61 0.69 a All the solvation free energies were obtained using the SMD model parameters and the IEF-PCM/Gaussian03 protocol for bulk electrostatics. N is the number of data in a given solute class.
S5 Table S2. Mean Signed Errors (kcal/mol) in Nonaqueous Solvation Free Energies, by Solute Class a solute class N M05-2X B3LYP HF MIDI!6D 6-31G* 6-31+G** cc-pvtz 6-31G* 6-31G* H 2, NH 3, H 2 O 29 0.62 1.27 1.62 0.94 1.01 1.39 unbranched alkanes 85 0.30 0.25 0.12 0.05 0.43 0.39 branched alkanes 7 0.45 0.40 0.30 0.27 0.50 0.46 cycloalkanes 13 0.01 0.01 0.10 0.12 0.11 0.08 alkenes 18 0.09 0.20 0.36 0.31 0.02 0.16 alkynes 9 0.34 0.55 0.70 0.72 0.26 0.64 arenes 134 0.44 0.50 0.71 0.54 0.15 0.46 alcohols 272 0.35 0.07 0.54 0.14 0.21 0.24 phenols 109 0.31 0.01 0.29 0.11 0.69 0.09 ethers 87 0.45 0.10 0.62 0.11 0.53 0.21 aldehydes 32 0.53 0.14 0.86 0.60 0.34 0.95 ketones 195 0.03 0.58 1.17 0.99 0.32 1.03 carboxylic acids 120 1.16 0.40 0.21 0.08 0.76 0.22 esters, including lactones b 243 0.61 0.17 0.31 0.14 0.42 0.12 peroxides 17 0.64 0.09 0.41 0.11 0.23 0.40 bifunctional H,C,O compounds 24 1.44 0.65 0.11 0.52 1.30 0.02 aliphatic amines 154 0.37 0.05 0.48 0.05 0.23 0.14 anilines 61 0.12 0.19 0.40 0.04 0.47 0.17 aromatic N-heterocycles (1 N) 52 0.29 0.00 0.44 0.14 0.51 0.21 aromatic N-heterocycles (2 Ns) 9 1.22 0.81 0.10 0.49 1.23 0.44 nitriles 20 0.15 0.46 0.93 0.88 0.22 1.01 hydrazines 5 0.87 0.16 0.97 0.18 0.25 0.27 bifunctional H,C,N compounds 2 0.55 1.51 2.50 1.73 0.63 2.39 amides 26 1.45 0.57 0.23 0.20 1.16 0.01 ureas 7 2.09 1.07 0.30 0.96 1.85 0.58 lactams 4 1.94 0.89 0.14 0.25 1.39 0.11 nitrohydrocarbons 86 0.68 0.07 0.61 0.24 0.51 0.88 bifunctional H,C,N,O compounds 3 1.32 0.72 0.23 0.56 1.31 0.38
S6 Table S2. Continued solute class N M05-2X B3LYP HF MIDI!6D 6-31G* 6-31+G** cc-pvtz 6-31G* 6-31G* fluoroalkanes 5 0.30 0.52 1.06 0.85 0.32 0.82 fluoroarenes 11 0.10 0.31 0.67 0.45 0.08 0.50 chloroalkanes 26 1.03 0.89 1.07 0.83 0.78 1.08 chloroalkenes 15 0.73 0.86 0.77 0.90 0.96 0.69 chloroarenes 31 0.35 0.32 0.53 0.28 0.11 0.47 bromoalkanes 21 0.47 0.74 0.96 0.83 0.57 0.80 bromoalkenes 2 0.44 0.83 1.17 0.94 0.50 0.94 bromoarenes 16 0.31 0.51 0.74 0.55 0.10 0.56 multihalogen hydrocarbons 14 0.23 0.21 0.05 0.16 0.27 0.04 halogenated bifunctional compounds 37 0.91 0.36 0.13 0.37 0.92 0.01 thiols 10 0.55 0.46 0.64 0.39 0.12 0.44 sulfides 13 0.69 0.62 0.82 0.57 0.30 0.57 disulfides 4 1.11 1.18 1.03 1.24 1.35 1.15 sulfur heterocycles 4 0.53 0.57 0.42 0.60 0.94 0.45 sulfoxides 1 1.53 0.27 1.56 0.36 1.07 0.92 phosphorus compounds 37 1.21 0.60 0.03 0.53 1.18 0.28 silicon compounds 2 1.95 1.83 1.66 1.65 2.03 1.86 all neutral data 2072 0.34 0.06 0.50 0.19 0.31 0.33 a All the solvation free energies were obtained using the SMD model parameters and the IEF-PCM/Gaussian03 protocol for bulk electrostatics. N is the number of data in a given solute class. b 5 lactones and 238 other esters
S7 Table S3. Mean Signed Errors (kcal/mol) in Transfer Free Energies between Water and Organic Solvents, by Solute Class a solute class N M05-2X B3LYP HF MIDI!6D 6-31G* 6-31+G** cc-pvtz 6-31G* 6-31G* lactones 10 0.40 0.29 0.70 0.31 0.14 1.73 aromatic N-heterocycles 6 0.05 0.08 0.33 0.14 0.33 0.21 bifunctional H,C,N compounds 2 0.69 0.84 0.98 0.87 0.71 0.92 amides 13 1.22 0.56 0.11 0.40 1.19 0.27 ureas 11 1.03 0.52 0.32 0.54 0.97 0.04 lactams 4 1.54 1.31 1.20 1.25 1.49 0.93 thymines and uracils 12 0.94 0.07 0.36 0.09 0.53 1.46 bifunctional H,C,N,O compounds 5 0.38 0.62 0.79 0.63 0.44 1.07 halogenated bifunctional compounds 39 0.50 0.04 0.37 0.15 0.29 0.90 sulfur compounds 19 0.15 0.01 0.08 0.01 0.13 0.27 phosphorus compounds 9 0.06 0.69 0.92 0.61 0.05 1.95 silicon compounds 13 0.10 0.00 0.06 0.02 0.18 0.05 all neutral data 143 0.48 0.02 0.24 0.04 0.38 0.71 a All the solvation free energies were obtained using the SMD model parameters and the IEF-PCM/Gaussian03 protocol for bulk electrostatics. N is the number of data in a given solute class.
S8 Table S4. Errors (kcal/mol) in Solvation and Transfer Free Energies for Neutrals, by Solvent a solvent N b ε α β MSE c MUE d acetic acid 7 6.25 0.61 0.44 1.93 1.93 acetonitrile 7 35.69 0.07 0.32 0.62 0.63 acetophenone 9 17.44 0.00 0.48 0.41 0.65 aniline 10 6.89 0.26 0.41 0.51 0.60 anisole 8 4.22 0.00 0.29 0.09 0.37 benzene 75 2.27 0.00 0.14 0.44 0.70 benzonitrile 7 25.59 0.00 0.33 0.78 0.79 benzyl alcohol 10 12.46 0.33 0.56 0.01 0.68 bromobenzene 27 5.40 0.00 0.09 0.75 0.76 bromoethane 7 9.01 0.00 0.12 0.74 0.78 bromoform 12 4.25 0.15 0.06 0.42 0.43 bromooctane 5 5.02 0.00 0.12 0.69 0.69 n-butanol 20 17.33 0.37 0.48 0.42 0.78 sec-butanol 9 15.94 0.33 0.56 0.45 0.68 butanone 13 18.25 0.00 0.51 0.62 0.99 butyl acetate 22 4.99 0.00 0.45 0.66 0.77 n-butylbenzene 10 2.36 0.00 0.15 0.36 0.41 sec-butylbenzene 5 2.34 0.00 0.16 0.19 0.24 t-butylbenzene 14 2.34 0.00 0.16 0.16 0.33 carbon disulfide 15 2.61 0.00 0.07 0.09 0.56 carbon tetrachloride 78 2.23 0.00 0.00 0.14 0.52 chlorobenzene 38 5.70 0.00 0.07 0.81 0.82 chloroform 105 4.71 0.15 0.02 0.03 0.84 chlorohexane 11 5.95 0.00 0.10 0.84 0.84 m-cresol 7 12.44 0.57 0.34 0.89 0.93 cyclohexane 91 2.02 0.00 0.00 0.18 0.51 cyclohexanone 10 15.62 0.00 0.56 0.25 0.84 decalin (mixture) 26 2.20 0.00 0.00 0.36 0.59 decane 39 1.98 0.00 0.00 0.07 0.39 decanol 11 7.53 0.37 0.48 0.35 0.66 1,2-dibromoethane 10 4.93 0.10 0.17 0.25 0.41 dibutyl ether 15 3.05 0.00 0.45 0.51 0.64 o-dichlorobenzene 11 9.99 0.00 0.04 1.16 1.16 1,2-dichloroethane 39 10.13 0.10 0.11 0.43 0.71 diethyl ether 67 4.24 0.00 0.41 0.14 0.78 diisopropyl ether 22 3.38 0.00 0.41 0.25 0.78 N,N-dimethylacetamide 7 37.78 0.00 0.78 0.11 0.60 N,N-dimethylformamide 7 37.22 0.00 0.74 0.03 0.56 2,6-dimethylpyridine 6 7.17 0.00 0.63 0.15 0.63 dimethyl sulfoxide 7 46.83 0.00 0.88 0.35 0.59 dodecane 8 2.01 0.00 0.00 0.06 0.34 ethanol 8 24.85 0.37 0.48 1.65 1.67 ethoxybenzene 7 4.18 0.00 0.32 0.12 0.30
S9 Table S4. Continued solvent N b ε α β MSE c MUE d ethyl acetate 21 5.99 0.00 0.45 0.50 0.71 ethylbenzene 29 2.43 0.00 0.15 0.08 0.40 fluorobenzene 7 5.42 0.00 0.10 0.93 0.93 1-fluoro-n-octane 6 3.89 0.00 0.10 0.33 0.34 heptane 66 1.91 0.00 0.00 0.03 0.39 heptanol 12 11.32 0.37 0.48 0.05 0.57 hexadecane 190 2.04 0.00 0.00 0.11 0.52 hexadecyl iodide 9 3.53 0.00 0.15 0.32 0.60 hexane 59 1.88 0.00 0.00 0.11 0.52 hexanol 14 12.51 0.37 0.48 0.12 0.66 iodobenzene 20 4.55 0.00 0.12 0.51 0.55 isobutanol 17 16.78 0.37 0.48 0.35 0.49 isooctane 32 1.94 0.00 0.00 0.43 0.52 isopropanol 7 19.26 0.33 0.56 1.27 1.31 isopropylbenzene 19 2.37 0.00 0.16 0.01 0.32 p-isopropyltoluene 6 2.23 0.00 0.19 0.47 0.47 mesitylene 7 2.27 0.00 0.19 0.08 0.35 methoxyethanol 6 17.20 0.30 0.84 0.13 0.82 methylene chloride 11 8.93 0.10 0.05 1.13 1.13 N-methylformamide 7 181.56 0.40 0.55 0.25 0.88 4-methyl,2-pentanone 13 12.89 0.00 0.51 0.48 0.93 2-methylpyridine 6 9.95 0.00 0.58 0.30 0.73 nitrobenzene 15 34.81 0.00 0.28 0.81 0.81 nitroethane 7 28.29 0.02 0.33 0.43 0.47 nitromethane 7 36.56 0.06 0.31 0.55 0.78 o-nitrotoluene 6 25.67 0.00 0.27 0.28 0.40 nonane 26 1.96 0.00 0.00 0.00 0.30 nonanol 10 8.60 0.37 0.48 0.07 0.55 octane 38 1.94 0.00 0.00 0.04 0.37 octanol 206 9.86 0.37 0.48 0.17 0.82 pentadecane 9 2.03 0.00 0.00 0.43 0.46 pentane 26 1.84 0.00 0.00 0.28 0.39 pentanol 22 15.13 0.37 0.48 0.26 0.76 perfluorobenzene 15 2.03 0.00 0.00 0.58 0.60 phenyl ether 6 3.73 0.00 0.20 1.18 1.18 propanol 7 20.52 0.37 0.48 1.11 1.19 pyridine 7 12.98 0.00 0.52 0.39 0.73 tetrachloroethene 10 2.27 0.00 0.00 0.56 0.70 tetrahydrofuran 7 7.43 0.00 0.48 0.17 0.49 tetrahydrothiophene dioxide 7 43.96 0.00 0.88 1.20 1.20 tetralin 9 2.77 0.00 0.19 1.04 1.16 toluene 51 2.37 0.00 0.14 0.25 0.46 tributyl phosphate 16 8.18 0.00 1.21 0.08 0.47
S10 Table S4. Continued solvent N b ε α β MSE c MUE d triethylamine 7 2.38 0.00 0.79 0.62 0.80 1,2,4-trimethylbenzene 11 2.37 0.00 0.19 0.28 0.40 undecane 13 1.99 0.00 0.00 0.07 0.53 water 274 78.36 n/a n/a 0.05 0.59 xylene (mixture) 48 2.39 0.00 0.16 0.34 0.49 benzene/water 4 2.27 0.00 0.14 1.28 1.28 n-butanol/water 1 17.33 0.37 0.48 0.53 0.53 carbon tetrachloride/water 2 2.23 0.00 0.00 1.45 1.45 chlorobenzene/water 1 5.70 0.00 0.07 0.12 0.12 chloroform/water 10 4.71 0.15 0.02 0.00 0.82 cyclohexane/water 5 2.02 0.00 0.00 0.55 0.79 1,2-dibromoethane/water 1 4.93 0.10 0.17 1.24 1.24 dibutyl ether/water 1 3.05 0.00 0.45 1.13 1.13 1,2-dichloroethane/water 3 10.13 0.10 0.11 0.03 0.54 diethyl ether/water 11 4.24 0.00 0.41 0.38 0.43 ethyl acetate/water 4 5.99 0.00 0.45 0.39 0.39 heptane/water 8 1.91 0.00 0.00 0.19 0.68 hexane/water 1 1.88 0.00 0.00 0.28 0.28 nitrobenzene/water 1 34.81 0.00 0.28 0.72 0.72 octanol/water 90 9.86 0.37 0.48 0.02 0.60 a ε is the solvent s dielectric constant; α is Abraham s hydrogen bond acidity parameter (which Abraham denotes as Σα 2 ); and β is Abraham s hydrogen bond basicity parameter (which Abraham denotes as Σβ 2 ). The SMD solvation energies were calculated at the M05-2X/6-31G* level of theory. b N is the number of neutral solute data in a given solvent. c Mean signed error d Mean unsigned error