Cluster-continuum quasichemical theory calculation of the lithium ion solvation in water, acetonitrile and dimethyl sulfoxide: an absolute single-ion solvation free energy scale

Carvalho, Nathália F.; Pliego, Josefredo R.

doi:10.1039/c5cp03798k

Cited by 66 publications

(77 citation statements)

References 97 publications

(126 reference statements)

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“…The Li + cation is mainly solvated by DMSO molecules at different concentration ratios of DMSO and ACN that is in qualitative agreement with the experiment . Cluster‐Continuum Quasichemical Theory calculations confirmed that the solvation free energy of Li + in DMSO is much more negative than in ACN and H 2 O . It was also shown that the solvation energy of Li + trended with solvent DN, and varied greater than that of O 2 − ions, which correlated with acceptor number .…”

Section: Introductionsupporting

confidence: 80%

“…[23] Cluster-Continuum Quasichemical Theory calculations confirmed that the solvation free energy of Li + in DMSO is much more negative than in ACN and H 2 O. [24] It was also shown that the solvation energy of Li + trended with solvent DN, and varied greater than that of O 2 À ions, which correlated with acceptor number. [25] Furthermore, a significant inhibition of the Li + and Cl À ionassociation reaction in pure DMSO was shown compared to the ion-aggregation in ACN.…”

Section: Introductionmentioning

confidence: 99%

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Effect of Cation Size on Solvation and Association with Superoxide Anion in Aprotic Solvents

Smirnov

Kislenko

2019

ChemPhysChem

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Influence of cation size on solvation strength, diffusion, and kinetics of the association reaction with anions O2− in aprotic solvents, such as acetonitrile and dimethyl sulfoxide, has been investigated by means of molecular dynamics simulations. The work is motivated by the need to understand the molecular nature of the solvent‐induced changes in capacity of Li‐air batteries. We have shown that the dependence of the solvation shell stability on the cation size has a maximum at a particular ion radius that corresponds to a solvent coordination number of 4. The shell stability maximum coincides with the diffusion coefficient minimum. The variation of the cation shell stability has a crucial impact on the kinetics of the cation‐O2− association. We have demonstrated that profound inhibition of the association reaction for Li+ in dimethyl sulfoxide is a result of the lock‐and‐key effect that cannot be described in the framework of Hard Soft Acid Base theory.

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Section: Introductionsupporting

confidence: 80%

Section: Introductionmentioning

confidence: 99%

Effect of Cation Size on Solvation and Association with Superoxide Anion in Aprotic Solvents

Smirnov

Kislenko

2019

ChemPhysChem

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“…Recently, the cluster‐continuum quasichemical approach was used to establish a theoretical single‐ion bulk solvation free energy scale in water, methanol, DMSO, and acetonitrile solvents . The lithium ion was used as reference to establish the scale, because in this case the assumptions of the cluster‐continuum method are accurate.…”

Section: Theorymentioning

confidence: 99%

Hybrid discrete‐continuum solvation methods

Pliego

Riveros

2019

WIREs Comput Mol Sci

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Hybrid discrete‐continuum approaches for solvation have been widely applied for diverse problems in chemistry suck as pKa calculation in aqueous and nonaqueous solvents, activation free energy barriers for ionic processes in solution, and surface reactions. A special version of this approach, the cluster‐continuum quasichemical model, has also been used for establishing a single‐ion solvation free energy scale in different solvents compatible with the tetraphenylarsonium tetraphenylborate assumption. The use of discrete‐continuum solvation methods can lead to meaningful improvement with respect to pure continuum solvation models for modeling diverse chemical process in solution. In the case of pKa calculations, there are cases where the root mean squared error is as large as 7 pKa units with pure continuum solvation model and becomes around 1 pKa unit with the hybrid approach. For complex reactions in solution, errors as large as 10 kcal/mol for activation free energies with the pure continuum approach can be substantially reduced with the inclusion of explicit solvent molecules. A discussion of the theory of hybrid discrete‐continuum methods is also presented and further development is expected in the coming years. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Software > Quantum Chemistry Molecular and Statistical Mechanics > Free Energy Methods

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“…In fact, ions in solution are much more difficult to describe and the problem of net potential felt by the ion generates different solvation free energy scales. 21,[36][37][38] However, even more important than predicting absolute solvation free energy values is to predict correct variation of the solvation free energy between transition states and reactants as well as between products and reactants. This ability would lead to reliable prediction of solvent effects on chemical reactions.…”

Section: Introductionmentioning

confidence: 99%

“…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.…”

Section: Introductionmentioning

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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Cluster-continuum quasichemical theory calculation of the lithium ion solvation in water, acetonitrile and dimethyl sulfoxide: an absolute single-ion solvation free energy scale

Cited by 66 publications

References 97 publications

Effect of Cation Size on Solvation and Association with Superoxide Anion in Aprotic Solvents

Effect of Cation Size on Solvation and Association with Superoxide Anion in Aprotic Solvents

Hybrid discrete‐continuum solvation methods

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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