Computation of methodology-independent single-ion solvation properties from molecular simulations. III. Correction terms for the solvation free energies, enthalpies, entropies, heat capacities, volumes, compressibilities, and expansivities of solvated ions

2011 ◽  
Vol 134 (14) ◽  
pp. 144103 ◽  
Author(s):  
Maria M. Reif ◽  
Philippe H. Hünenberger
Keyword(s):  
Molecular Simulations ◽  
Heat Capacities ◽  
Ion Solvation ◽  
Free Energies ◽  
Solvated Ions ◽  
Solvation Free Energies ◽  
Correction Terms

scholarly journals The Born Model Can Accurately Describe Electrostatic Ion Solvation.

2020 ◽  
Author(s):  
Timothy Duignan ◽  
Xiu Song Zhao
Keyword(s):  
Electrolyte Solutions ◽  
Ion Solvation ◽  
Water Model ◽  
Repulsive Interaction ◽  
Free Energies ◽  
Hydrogen Atoms ◽  
Ionic Charge ◽  
Born Model ◽  
Reasonable Choice ◽  
Solvation Free Energies

<p>Accurate models of the free energies of ions in solution are crucial for understanding and modelling the huge number of important applications where electrolyte solutions play a crucial role such as electrochemical energy storage. The Born model, developed to describe ion solvation free energies, is widely considered to be critically flawed as it predicts a linear response of water to ionic charge, which fails to match water's supposed intrinsic preference to solvate anions over cations. Here, we demonstrate that this asymmetric response observed in simulation is the result of an arbitrary choice that the oxygen atom should be the centre of a water molecule. We show that an alternative and reasonable choice, which places the centre 0.5 Å towards the hydrogen atoms, results in a linear and charge symmetric response of water to ionic charge for a classical water model consistent with the Born model. This asymmetry should therefore be regarded as a property of the short range repulsive interaction not an intrinsic electrostatic property of water. We also show that this new water centre results in a more reasonable neutral cavity potential. </p><p></p>

scholarly journals Approaches for calculating solvation free energies and enthalpies demonstrated with an update of the FreeSolv database

2017 ◽  
Author(s):  
Guilherme Duarte Ramos Matos ◽  
Daisy Y. Kyu ◽  
Hannes H. Loeffler ◽  
John D. Chodera ◽  
Michael R. Shirts ◽  
...  
Keyword(s):  
Free Energy ◽  
Organic Molecules ◽  
Molecular Simulations ◽  
General Purpose ◽  
Free Energies ◽  
Energy Functions ◽  
Neutral Compounds ◽  
Aqueous Solvation ◽  
Solvation Free Energies

AbstractSolvation free energies can now be calculated precisely from molecular simulations, providing a valuable test of the energy functions underlying these simulations. Here, we briefly review “alchemical” approaches for calculating the solvation free energies of small, neutral organic molecules from molecular simulations, and illustrate by applying them to calculate aqueous solvation free energies (hydration free energies). These approaches use a non-physical pathway to compute free energy differences from a simulation or set of simulations and appear to be a particularly robust and general-purpose approach for this task. We also present an update (version 0.5) to our FreeSolv database of experimental and calculated hydration free energies of neutral compounds and provide input files in formats for several simulation packages. This revision to FreeSolv provides calculated values generated with a single protocol and software version, rather than the heterogeneous protocols used in the prior version of the database. We also further update the database to provide calculated enthalpies and entropies of hydration and some experimental enthalpies and entropies, as well as electrostatic and nonpolar components of solvation free energies.

scholarly journals The Born model can accurately describe electrostatic ion solvation

2020 ◽  
Vol 22 (43) ◽  
pp. 25126-25135
Author(s):  
Timothy T. Duignan ◽  
X. S. Zhao
Keyword(s):  
Oxygen Atom ◽  
Linear Response ◽  
Ion Solvation ◽  
Response Model ◽  
Free Energies ◽  
Born Model ◽  
Repulsion Force ◽  
Solvation Free Energies

The solvation free energies of ions in water are consistent with the Born linear response model if the centre on which the ion–water repulsion force acts is moved from the oxygen atom towards the hydrogens.

scholarly journals Real single ion solvation free energies with quantum mechanical simulation

2017 ◽  
Vol 8 (9) ◽  
pp. 6131-6140 ◽  
Author(s):  
Timothy T. Duignan ◽  
Marcel D. Baer ◽  
Gregory K. Schenter ◽  
Christopher J. Mundy
Keyword(s):  
Ion Pairs ◽  
Electrolyte Solutions ◽  
Ion Solvation ◽  
Quantum Mechanical ◽  
Free Energies ◽  
Ongoing Debate ◽  
Mechanical Simulation ◽  
Solvation Free Energies

Single ion solvation free energies are one of the most important properties of electrolyte solutions and yet there is ongoing debate about what these values are. Only the values for neutral ion pairs are known.

scholarly journals Resolving solvophobic interactions inferred from experimental solvation free energies and evaluated from molecular simulations

2017 ◽  
Vol 667 ◽  
pp. 62-67 ◽  
Author(s):  
J. Wesley Barnett ◽  
Amna Bhutta ◽  
Sarah C. Bierbrier ◽  
Natalia da Silva Moura ◽  
Henry S. Ashbaugh
Keyword(s):  
Molecular Simulations ◽  
Free Energies ◽  
Solvophobic Interactions ◽  
Solvation Free Energies

scholarly journals 1-Octanol/Water Partition Coefficients of n-Alkanes from Molecular Simulations of Absolute Solvation Free Energies

2009 ◽  
Vol 5 (9) ◽  
pp. 2436-2446 ◽  
Author(s):  
Nuno M. Garrido ◽  
António J. Queimada ◽  
Miguel Jorge ◽  
Eugénia A. Macedo ◽  
Ioannis G. Economou
Keyword(s):  
Partition Coefficients ◽  
Molecular Simulations ◽  
Free Energies ◽  
Solvation Free Energies
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