A scaled particle theory of aqueous and nonaqueous solutions

Pierotti, Robert A.

doi:10.1021/cr60304a002

Cited by 1,277 publications

(962 citation statements)

References 30 publications

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“…Solvation effects were calculated with the integral equation formalism of the polarizable continuum model (IEF-PCM) [13] by computing B3LYP single-point ener-gies. Cavitation energies were computed via the method of Pierotti and Claverie, [13,14] while repulsion and dispersion energies were determined by the procedure of Amovilli and Mennucci [15].…”

Section: Theoreticalmentioning

confidence: 99%

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An experimental and theoretical investigation into the hydrolysis of dichloro(ethylenediamine)platinum(II) via electrospray mass spectrometry and density functional theory

Yoshikawa

Bach

Merrill

2009

J. Am. Soc. Mass Spectrom.

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Dichloro(ethylenediamine)platinum(II), Pt(en)Cl 2 , was dissolved in H 2 O and D 2 O, and the resulting aqueous solutions were electrosprayed into a quadrupole ion-trap mass spectrometer. A series of major and minor ionic hydrolysis products were detected. These ions were then subjected to collision-induced dissociation. As an aid in interpreting the experimental results, density functional theory calculations were carried out. These computations permitted the structures and energetics associated with the hydrolysis products to be determined. An understanding of the hydrolysis of PtenCl 2 and related coordination complexes is essential in the rational design of metal-based drugs. (J Am Soc Mass Spectrom 2009, 20, 1015-1029

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Section: Theoreticalmentioning

confidence: 99%

“…Cavitation energies were computed via the method of Pierotti and Claverie, [13,14] while repulsion and dispersion energies were determined by the procedure of Amovilli and Mennucci [15]. Solute electron charge density that escaped from the solvent cavity was explicitly treated by the method of Mennucci and Tomasi [16].…”

Section: Theoreticalmentioning

confidence: 99%

An experimental and theoretical investigation into the hydrolysis of dichloro(ethylenediamine)platinum(II) via electrospray mass spectrometry and density functional theory

Yoshikawa

Bach

Merrill

2009

J. Am. Soc. Mass Spectrom.

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“…However, in addition to such energetical considerations the hydration entropy of small simple solutes is found to be negative, which is usually explained as increased ordering of the molecules in the hydration shell [4,5]. This is the characteristic feature of the so called hydrophobic hydration of small apolar particles [6,7]. As a consequence, with increasing temperature the association of hydrophobic particles is found to be enhanced in order to minimise the solvation entropy penalty [8,9].…”

Section: Introductionmentioning

confidence: 99%

Temperature dependence of the hydrophobic hydration and interaction of simple solutes: An examination of five popular water models

Paschek

2004

The Journal of Chemical Physics

274

326

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We examine five different popular rigid water models (SPC, SPCE, TIP3P, TIP4P and TIP5P) using molecular dynamics simulations in order to investigate the hydrophobic hydration and interaction of apolar Lennard-Jones solutes as a function of temperature in the range between 275 K and 375 K along the 0.1 MPa isobar. For all investigated models and state points we calculate the excess chemical potential for the noble gases and Methane employing the Widom particle insertion technique. All water models exhibit too small hydration entropies, but show a clear hierarchy. TIP3P shows poorest agreement with experiment whereas TIP5P is closest to the experimental data at lower temperatures and SPCE is closest at higher temperatures. As a first approximation, this behaviour can be rationalised as a temperature-shift with respect to the solvation behaviour found in real water. A rescaling procedure inspired by information theory model of Hummer et al. (Chem.Phys. 258, 349-370 (2000)) suggests that the different solubility curves for the different models and real water can be largely explained on the basis of the different density curves at constant pressure. In addition, the models that give a good representation of the water structure at ambient conditions (TIP5P, SPCE and TIP4P) show considerably better agreement with the experimental data than the ones which exhibit less structured O-O correlation functions (SPC and TIP3P). In the second part of the paper we calculate the hydrophobic interaction between Xenon particles directly from a series of 60 ns simulation runs. We find that the temperature dependence of the association is to a large extent related to the strength of the solvation entropy. Nevertheless, differences between the models seem to require a more detailed molecular picture. The TIP5P model shows by far the strongest temperature dependence. The suggested density-rescaling is also applied to the chemical potential in the Xenon-Xenon contact-pair configuration, indicating the presence of a temperature where the hydrophobic interaction turns into purely repulsive. The predicted association for Xenon in real water suggest the presence a strong variation with temperature, comparable to the behaviour found for TIP5P water. Comparing different water models and experimental data we conclude that a proper description of density effects is an important requirement for a water model to account correctly for the correct description of the hydrophobic effects. A water model exhibiting a density maximum at the correct temperature is desirable.

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“…To do this, the enthalpy of solvation can be considered as a sum of two terms: the enthalpy needed for creating a cavity in the solvent to hold the solute molecule, D cav H, and the enthalpy corresponding to the intermolecular forces up by the solute in solution, D int H 0 . This term is related to D solv H 0 by the following expression [11] …”

Section: Resultsmentioning

confidence: 99%

Enthalpy of solvation of butanediols in different solvents

et al. 2000

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The enthalpies of solution for 1,2-, 1,3-, 1,4-and 2,3-butanediol in water, formamide and dimethylsulphoxide were determined by calorimetry. From the results and data available in the literature for the enthalpy of vaporisation, the enthalpy of solvation was determined. The enthalpy of solvation was decomposed into two terms, cavity formation in the solvent to hold the solute and solute±solvent interaction. #

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A scaled particle theory of aqueous and nonaqueous solutions

Cited by 1,277 publications

References 30 publications

An experimental and theoretical investigation into the hydrolysis of dichloro(ethylenediamine)platinum(II) via electrospray mass spectrometry and density functional theory

An experimental and theoretical investigation into the hydrolysis of dichloro(ethylenediamine)platinum(II) via electrospray mass spectrometry and density functional theory

Temperature dependence of the hydrophobic hydration and interaction of simple solutes: An examination of five popular water models

Enthalpy of solvation of butanediols in different solvents

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