Modeling short-range contributions to hydration energies with minimal parameterization

Pomogaeva, Anna V.; Thompson, Daniel W.; Chipman, Daniel M.

doi:10.1016/j.cplett.2011.05.063

Cited by 23 publications

(40 citation statements)

References 49 publications

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“…We note the limitation that the present version of the model only allows for treatment of the single strongest donor and single strongest acceptor sites on the solute, as discussed previously. 54,55 For cyclohexane and benzene solvents, it was found 48 that ΔG FESR made negligible contributions, as expected since those solvents have little propensity for hydrogen bonding interactions. The implicit solvation model described as SS(V)PE+disp+exch that was presented for cyclohexane and benzene 48 may therefore be regarded as the CMIRS1.0 model for those solvents where the C and D parameters both happen to have values of zero.…”

Section: ■ Methodsmentioning

confidence: 82%

Composite Method for Implicit Representation of Solvent in Dimethyl Sulfoxide and Acetonitrile

Pomogaeva

Chipman

2014

J. Phys. Chem. A

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A composite method for implicit representation of solvent previously developed to compute aqueous free energies of solvation is extended to accommodate the polar aprotic solvents dimethyl sulfoxide and acetonitrile. The method combines quantum mechanical calculation of the solute electronic structure with a modern dielectric continuum model for long-range electrostatic interactions with solvent and individual models for short-range interactions arising from dispersion, exchange, and hydrogen bonding. The few parameters involved are optimized to fit a standard data set of experimental solvation energies for neutrals and ions. Results are better than other models in the literature, with average errors for ions comparable to or smaller than the estimated experimental errors. Some circumstantial evidence is also obtained to support one of the competing extrathermodynamic arguments recently used to determine the solvation energies of the proton, which are needed to separate measurements of paired cation plus anion solvation energies into absolute single ion solvation energies in these solvents.

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Section: ■ Methodsmentioning

confidence: 82%

Composite Method for Implicit Representation of Solvent in Dimethyl Sulfoxide and Acetonitrile

Pomogaeva

Chipman

2014

J. Phys. Chem. A

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“…Also in this case, a nonlocal definition of the interface may be used to overcome such a limitation. Alternatively, local interfaces that also depend on the electrostatic field [48,50,94,95] have been proposed in the literature and were shown to improve the description of charged systems.…”

Section: Local Vs Nonlocal Interfacesmentioning

confidence: 99%

Continuum embeddings in condensed‐matter simulations

Andreussi

Fisicaro

2018

Int J of Quantum Chemistry

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Continuum models have a long tradition in computational chemistry, where they have provided a compact and efficient way to characterize environment effects in quantum-mechanical simulations of solvated systems. Fattebert and Gygi pioneered the development of continuum dielectric embedding schemes for periodic systems and their seamless extension toward molecular dynamics simulations. Following their work, continuum embedding approaches in condensedmatter simulations have thrived. The possibility to model wet and electrified interfaces, with a reduced computational overhead with respect to isolated systems, is opening new perspectives in the characterization of materials and devices. Important applications of these new techniques are in the field of catalysis, electro-chemistry, electro-catalysis, etc. Here we will address the main physical and computational aspects of continuum embedding schemes recently developed for condensed-matter simulations, underlying their peculiarities and their differences with respect to the quantum-chemistry state-of-the-art.condensed matter, continuum models, electro-chemistry, materials, solvation 1 | INTRODUCTION An embedding liquid environment can substantially affect the electronic properties, geometries and spectroscopic responses of the embedded system. Dealing with this kind of effects is a difficult computational task, due to the multiscale nature of the system. A brute force approach to handle these effects would require including all of the solvent atomistic details in the quantum-mechanical (QM) calculation of the solvated system. The total number of degrees of freedom, in particular the number of electrons that need to be described in a first-principles calculation, can thus increase by orders of magnitude. As a result, a calculation that would be feasible in vacuum can easily become untreatable in solution. Moreover, statistical sampling and averaging of the results over different configurations of the liquid would be required, thus further increasing the computational cost of such an approach. These limitations have motivated the development of incredibly powerful simulation programs, [1][2][3] able to take advantage of the rapid evolution of scientific computing hardware and software, for example, by fully exploiting parallel and hybrid architectures. Regardless of its computational feasibility, the explicit description of liquid environments may also suffer from some well-known limitations of current state-of-the-art ab initio methods, in particular regarding their structural [4][5][6][7] and dielectric [8][9][10] properties.On the other hand, when looking at the properties of a solvated system, it is often the case that the detailed effects caused by solute-solvent interactions are less important than the intrinsic properties of the solute. If this is the case, one can exploit a hierarchical approach, where solvent degrees of freedom are treated with a computationally less expensive technique, but are coupled with an highly accurate description of the solvated system...

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“…For example, the COSMO-RS model 56,57 has been tested for proton exchange and recombination reactions with reasonable accuracy. 58 Other promising approaches are the SMVLE 59 and CMIRS [60][61][62] methods. Essentially, these methods include a term to describe the effect of extremum electric field generated by charged solutes.…”

Section: Resultsmentioning

confidence: 99%

How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents?

Miguel¹,

Santos²,

Silva³

et al. 2016

Journal of the Brazilian Chemical Society

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In the past seven years, the SMD (Solvent Model Density) method has been widely used by computational chemists. Thus, assessment on the reliability of this model for modeling chemical process in solution is worthwhile. In this report, it was investigated six anion-molecule nucleophilic substitution reactions in methanol and dipolar aprotic solvents. Geometry optimizations have been done at SMD/X3LYP level and single point energy calculations at CCSD(T)/TZVPP + diff level. Our results have indicated that the SMD model is not adequate for dipolar aprotic solvents, with a root of mean squared (RMS) error of 5.6 kcal mol . The classical protic to dipolar aprotic solvent rate acceleration effect was not predicted by the SMD model for the tested systems.Keywords: continuum solvation model, ion solvation, solvent effect, aromatic nucleophilic substitution, M11 functional IntroductionIn the middle of the twentieth century, several experimental studies have led to foundation of empirical rules for qualitative prediction of solvent effects on chemical reactions, authoritatively reviewed by Parker 1 in a classical paper. Nevertheless, a deeper view on solvent effects was only possible with experimental studies of gas phase ion-molecule reactions [2][3][4][5][6] and theoretical modeling of these processes. [7][8][9] It was evident from theoretical studies that solute-solvent interactions can be very strong and produce a profound effect on chemical reactivity. [10][11][12][13][14][15][16][17] On the other hand, gas phase dynamic of chemical reactions can open new mechanistic possibilities. 18,19 Among the different solvents used to conduct ionic chemical reactions, polar protic and dipolar aprotic solvents are paramount due to their property of solubilize ionic species. 20 Methanol is a polar protic solvent and its ability to solvate ions is similar to water. 21,22 In addition, it has the advantage of solubilize many organic molecules not soluble in water. Some usual dipolar aprotic solvents are dimethyl sulfoxide (DMSO), dimethylformamide (DMF) and acetonitrile. Because anions are less solvated in these solvents, anion-molecule reactions are accelerated when transferred from protic to dipolar aprotic solvents. Our ability to describe theoretically this effect is an important goal and a challenge for continuum solvation models once requires these models be able to describe specific solutesolvent interactions. 23 Considering that the Born formula for solvation of a spherical ion of charge q and radius R into a solvent with dielectric constant ε is given by:(1) it could be noted that the use of the same "molecular cavity" for an ionic solute into a protic and dipolar aprotic solvent with high dielectric constant would lead to very similar solvation free energy of ions. A possibility to overcome this problem would be to use different molecular cavity for protic and dipolar aprotic solvents. This approach has reached some successful ten years ago using the polarizable continuum model (PCM) in the study of anion-molecule reaction...

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Modeling short-range contributions to hydration energies with minimal parameterization

Cited by 23 publications

References 49 publications

Composite Method for Implicit Representation of Solvent in Dimethyl Sulfoxide and Acetonitrile

Composite Method for Implicit Representation of Solvent in Dimethyl Sulfoxide and Acetonitrile

Continuum embeddings in condensed‐matter simulations

How Accurate is the SMD Model for Predicting Free Energy Barriers for Nucleophilic Substitution Reactions in Polar Protic and Dipolar Aprotic Solvents?

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