New Solvation Radii for CPCM Solvation Radii Ranges and Comparing

Gibb’s Solvation Energies

Solvation Model: Addition of Nitrogen A total of 565 molecules containing carbon,
Ruveid Rizvic and Dr. Adam Moser hydrogen, oxygen, and nitrogen were obtained from the
Loras Solvation Database. Out of these molecules,
SOLVATION AND IMPLEMENTING GOAL
there were 475 neutral, 48 cation, and 42 anion
IMPLICIT SOLVATION MODELS
molecules. There were 420 solvation radii
Solutions, where solutes dissolve in a solvent, are To generate new solvation radii for carbon, hydrogen,
combinations determined through the radii size of
important as it is present in most chemical and biological
oxygen, and nitrogen using CPCM solvation model to use as a each unique atom. The solvation radii ranges (in
processes. The process of solvation can be represented
through implicit solvation models. In these models, the angstroms) are listed below in increment changes of
solute is represented through quantum chemistry. CPCM foundation to narrow down radii search ranges for future 0.1 angstroms.
(Conductor-like Polarizable Continuum Model) is one of C H O N
the implicit solvation models where the solvent is research and to find the best definitions for subgroups. 1.7 – 2.1 1.0 – 1.2 1.4 – 1.7 1.4 – 2.0
represented as a dielectric field that surrounds the
RESULTS Solvation radii range for each unique atom. The size is measured in
angstroms.
solute.
Calculating Gibb’s Solvation Energy for solutes using
9 new solvation radii definitions were determined for 565 HF/6-31G(d) in Gaussian16 software:
molecules. Some radii definitions proved to work better for specific
∆solvG = ∆aqG - ∆gasG
molecule types.
Calculating error between experimental and calculated
Radii Combos Errors Failures
solvation energy:
C H O N MSE MUE RMSD NEUTRAL CATION ANION
Figure 1. Solvation radii comparison to cavity and radii definition. 1.7 1.1 1.4 1.5 -0.90 2.33 3.26 36 4 1
Error = ∆solvG (exp) - ∆solvG (calc)
1.7 1.1 1.4 1.6 -0.66 2.22 3.10 34 4 1
The space between the solute and solvent is known as
1.8 1.1 1.4 1.5 -0.68 2.11 3.10 31 5 1 Molecules with MSE ≥ 1, non-sensible atom size
the solvation cavity. The overlapping spheres is
1.8 1.1 1.4 1.6 -0.47 2.04 2.98 29 4 1 combinations, and fails ≥20% of total molecule types
represented as the solute atom’s solvation radii. The
1.9 1.1 1.4 1.5 -0.10 1.99 3.09 20 6 2 were excluded from analysis.
size of the radii for each atom is proportional to the size
of the solvation cavity. Radii definitions contribute to
1.9 1.1 1.4 1.6 0.09 1.98 3.01 19 6 2 CONCLUSION
2 1 1.4 1.5 -0.80 2.39 3.44 28 7 5
the molecule’s set of solvation radii. This research concluded in finding 9 new solvation radii
2 1 1.4 1.6 -0.58 2.30 3.28 27 6 5
definitions for molecules containing carbon, hydrogen,
PROBLEM 2 1.1 1.4 1.5 0.83 2.22 3.41 24 7 7 oxygen, and nitrogen where cations and anions had less
Existing default radii definitions (UFF, Bondi, Pauling) Table 2. The resulting 9 radii definitions. These radii definitions listed are the result of excluding radii than 10 failed molecules. The following goals are
definitions that were not within ± 1 MSE, ± 3 MUE, and ±4 RMSD, as well as excluding radii definitions
could not accurately replicate solvation as they were not that did not represent the reality of molecules. complete:
1) Narrowing down radii search ranges:
constructed for solvation modeling. C H O N MSE MUE RMSD
DEFINITION C H O N 1.8 1.1 1.4 1.6 -0.98 1.79 2.48 All other molecule types C H O N
1.9 1.1 1.4 1.5 -0.70 1.61 2.36 did not contain radii
UFF 1.9255 1.443 1.75 1.83 1.7 – 2.1 1.0 – 1.2 1.3 – 1.4 1.5 – 1.6
1.9 1.1 1.4 1.6 -0.54 1.57 2.23 definitions within ± 1 MSE,
BONDI 1.5 1.2 1.4 1.55
2 1.1 1.4 1.5 0.11 1.65 2.33 ± 3 MUE, and ±4 RMSD, 2) Best performing solvation radii definitions for all
PAULING 1.7 1.2 1.52 1.5 Table 3. Resulting 4 radii definitions for neutrals. These
radii definitions listed are the result of excluding radii
and represented reality of molecules:
Neutrals performed well for Bondi and Pauling; however, definitions that were not within ± 1 MSE, ± 3 MUE, and ±4 atom size ratios.
RMSD, as well as excluding radii definitions that did not
C H O N
ion errors were not acceptable with these radii definitions. represent the reality of molecules.
With NE UFF Bondi Pauling UFF Bondi Pauling UFF Bondi Pauling 1.9 1.1 1.4 1.5
Neutrals Cations Anions
1.9 1.1 1.4 1.6
MSE 6.83 0.93 0.56 18.88 5.77 4.31 15.88 5.20 1.54 Carbon 1.7, Hydrogen 1.1, Oxygen 1.4, Nitrogen Carbon 1.8, Hydrogen 1.1, Oxygen 1.5, Nitrogen
1.5 1.6 20
MUE 6.83 2.02 2.60 18.88 5.98 4.80 15.88 6.39 4.25 20
FUTURE WORK
Calculated Solvation Energy (kcal/mol)

Calculated Solvation Energy (kcal/mol)

0
RMSE 7.57 2.49 3.29 19.40 7.29 6.26 17.42 7.81 5.27 -120 -100 -80 -60 -40 -20
0
0 20
-120 -100 -80 -60 -40 -20 0 20
Future research would be to include more molecules
Table 1. Neutral, Cation, and Anion Errors for the three default solvation radii definitions -20
-20
from the Loras Solvation Database by expanding the
with non-electrostatics on. The Mean Signed Errors (MSE), Mean Unsigned Errors (MUE),
and Root Mean Squared Errors (RMSE) are listed under each radii definition. -40 -40 molecular search range by adding one unique atom at
a time. Narrowing down solvation radii ranges, with
CURRENT SOLVATION DEFINITIONS -60 -60
nitrogen-containing molecules included, should be done
-80 -80
in smaller increments (possibly 0.05 angstroms).
11 New solvation radii were identified for 354 molecules -100 -100 Looking at smaller oxygen sizes could prove to show
within ±1 MSE, ±3 MUE, and ±4 RMSD: 315 neutrals, 32 better results for anions.
-120 -120
anions, 7 cations. Increasing oxygen radii size drastically Experimental Solvation Energy (kcal/mol)
Figure 2. The error between Gibb's Experimental and Calculated
Experimental Solvation Energy (kcal/mol)
Figure 3. The error between Gibb's Experimental and Calculated REFERENCES
increased the number of failed ions while decreased solvation energies for Carbon 1.7, Hydrogen 1.1, Oxygen 1.4, and solvation energies for Carbon 1.8, Hydrogen 1.1, Oxygen 1.5, and
Nitrogen 1.5. Neutrals (blue), cations (grey), and anions (orange) Nitrogen 1.6. Neutrals (blue), cations (grey), and anions (orange) are 1. Cramer, C. J.; Truhlar, D. G. Implicit Solvation Models: Equilibria, Structure,
neutral molecule fails. The solvation radii ranges were: are plotted along the experimental and calculated Gibb's Solvation plotted along the experimental and calculated Gibb's Solvation
Spectra, and Dynamics. Chem. Rev. 1999, 99 (8), 2161–2200.
energy axis. This radii definition performed well for anions with energy axis. This radii definition performed well for neutrals with
• Carbon 1.4 – 2.1 angstroms 1/42 anions failing. 36/475 neutrals and 4/48 cations failed. 16/475 failing. Anions performed worse with 10/42 molecules https://doi.org/10.1021/cr960149m.
failing. 4/48 cations failed. 2. Sloan Neuzil. Benchmarking Boundary Definitions of the CPCM Implicit
• Oxygen 1.3 -1.9 angstroms Solvation Model, Loras College, Dubuque, IA, 2019.
This research is supported by: Chemistry and Biology Department, Computational Lab,
• Hydrogen 1.0 – 1.5 angstroms research peers Emma Hoefer and Nicholas Haskin, and research mentor Dr. Adam Moser. 3. Haskin, Nicholas. Loras College, Dubuque, IA, 2022.

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