Benchmarking Free Energy Calculations in Liquid Aliphatic Ketone Solvents Using the 3D-RISM-KH Molecular Solvation Theory
Abstract
:1. Introduction
2. Materials and Methods
3. Results
3.1. Molecular Simulations of Pure Liquid Ketones
3.2. Solvation Free Energy Calculations
3.3. Ketone–Water Partition Coefficient Calculations Using the 3D-RISM-KH Theory
4. Discussion
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
Abbreviations
3D-RISM | 3-Dimensional reference interaction site model |
AM1 | Austin model 1 |
CyO | Cyclohexanone |
GAFF | Generalized amber force field |
GF | Gaussian fluctuation |
KH | Kovalenko–Hirata closure |
MAD | Mean absolute deviation |
MD | Molecular dynamics |
MEK | 2-Butanone a.k.a. methyl ethyl ketone |
MIBK | Methyl isobutyl ketone |
PMV | Partial molar volume |
QM | Quantum mechanical |
RDF | Radial distribution function |
RMSE | Relative mean square error |
SFE | Solvation free energy |
References
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Atomic Site | σ (Å) | ε (kcal·mol−1) |
---|---|---|
C[H3] | 3.775 | 0.207 |
C[H2] | 3.905 | 0.118 |
C[H] | 3.850 | 0.080 |
C[=O] | 3.399 | 0.086 |
O[=C] | 2.960 | 0.210 |
OWater | 3.116 | 0.155 |
HWater | 0.700 | 0.046 |
C[H2]Cyclohexanone | 4.700 | 0.140 |
Molecule | Density (Experimental, gm/cm3) | Density (MD, gm/cm3) 1 | Dielectric Constant (Experimental) |
---|---|---|---|
Acetone | 0.784 | 0.782 (±0.0009) | 20.493 |
MEK | 0.805 | 0.784 (±0.0006) | 18.246 |
MIBK | 0.796 | 0.800 (±0.0003) | 12.887 |
CyO | 0.942 | 0.929 (±0.0008) | 15.619 |
Molecule | A (kcal·mol−1·Å−3) | B (kcal·mol−1) |
---|---|---|
Acyclic aliphatic ketone | 0.0016 | −4.2669 |
Cyclohexanone | −0.2286 | −5.0964 |
Compound | Solvent | ΔG(Exptl.) 1 | ΔG(CPCM) 2 | ΔG(SMD) 3 | ΔG(RISM) 4 |
---|---|---|---|---|---|
n-octane | Cyclohexanone | −4.57 | −0.64 | −4.13 | −3.37 |
Toluene | Cyclohexanone | −5.05 | −2.88 | −6.43 | −4.45 |
Ethanol | Cyclohexanone | −4.41 | −3.09 | −3.83 | −5.02 |
1,4-dioxane | Cyclohexanone | −4.95 | −3.37 | −5.30 | −7.02 |
2-butanone | Cyclohexanone | −4.42 | −2.35 | −5.27 | −5.32 |
Acetic acid | Cyclohexanone | −6.43 | −4.60 | −6.03 | −6.32 |
Propanoic acid | Cyclohexanone | −7.18 | −4.30 | −6.42 | −6.24 |
Nitromethane | Cyclohexanone | −5.09 | −5.42 | −5.77 | −6.70 |
Cyclohexanone | Cyclohexanone | −6.25 | −4.12 | −7.99 | −6.64 |
Hydrogen peroxide | Cyclohexanone | −9.11 | −4.60 | −7.62 | −6.39 |
n-octane | Butanone | −4.64 | −0.64 | −5.21 | −2.26 |
Toluene | Butanone | −5.06 | −2.90 | −7.26 | −3.71 |
Ethanol | Butanone | −4.46 | −3.13 | −4.34 | −4.46 |
1,4-dioxane | Butanone | −5.02 | −3.41 | −5.96 | −6.29 |
Formaldehyde | Butanone | −1.77 | −3.17 | −3.22 | −4.82 |
2-butanone | Butanone | −4.5 | −2.40 | −5.96 | −4.71 |
Acetic acid | Butanone | −6.88 | −4.65 | −6.51 | −5.99 |
Propanoic acid | Butanone | −7.05 | −4.35 | −7.00 | −5.88 |
Butanoic acid | Butanone | −7.34 | −4.40 | −7.63 | −5.83 |
Pentanoic acid | Butanone | −7.54 | −4.55 | −8.37 | −5.80 |
Hexanoic acid | Butanone | −8.07 | −4.61 | −9.09 | −5.76 |
Nitromethane | Butanone | −5.24 | −5.49 | −6.37 | −6.15 |
γ-butyrolactone | Butanone | −4.47 | −6.50 | −9.69 | −8.12 |
Naphthalene | Methyl isobutyl ketone | −7.45 | −2.55 | −8.29 | −7.26 |
Phenol | Methyl isobutyl ketone | −9.38 | −3.98 | −7.86 | −7.13 |
m-Cresol | Methyl isobutyl ketone | −8.79 | −4.24 | −8.15 | −7.27 |
Acetic acid | Methyl isobutyl ketone | −6.33 | −4.53 | −6.35 | −6.49 |
Propanoic acid | Methyl isobutyl ketone | −6.85 | −4.23 | −6.89 | −6.68 |
Butanoic acid | Methyl isobutyl ketone | −7.44 | −4.28 | −7.55 | −6.98 |
Trimethylamine | Methyl isobutyl ketone | −2.86 | −1.46 | −3.44 | −5.08 |
Diethylamine | Methyl isobutyl ketone | −3.63 | −1.99 | −4.86 | −5.01 |
Pyridine | Methyl isobutyl ketone | −5.33 | −3.11 | −6.36 | −6.37 |
Aniline | Methyl isobutyl ketone | −7.54 | −4.03 | −8.50 | −7.25 |
Ammonia | Methyl isobutyl ketone | −2.52 | −3.15 | −3.57 | −3.80 |
Methylamine | Methyl isobutyl ketone | −4.14 | −2.55 | −3.45 | −4.25 |
4-methyl-2-pentanone | Methyl isobutyl ketone | −5.23 | −3.74 | −7.39 | −6.18 |
MAD 5 | 2.41 | 0.98 | 1.21 | ||
RMSE 6 | 2.71 | 1.33 | 1.51 |
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Roy, D.; Kovalenko, A. Benchmarking Free Energy Calculations in Liquid Aliphatic Ketone Solvents Using the 3D-RISM-KH Molecular Solvation Theory. J 2021, 4, 604-613. https://doi.org/10.3390/j4040044
Roy D, Kovalenko A. Benchmarking Free Energy Calculations in Liquid Aliphatic Ketone Solvents Using the 3D-RISM-KH Molecular Solvation Theory. J. 2021; 4(4):604-613. https://doi.org/10.3390/j4040044
Chicago/Turabian StyleRoy, Dipankar, and Andriy Kovalenko. 2021. "Benchmarking Free Energy Calculations in Liquid Aliphatic Ketone Solvents Using the 3D-RISM-KH Molecular Solvation Theory" J 4, no. 4: 604-613. https://doi.org/10.3390/j4040044