Ab Initio Study of the Stabilization of Multiply Charged Anions in Water

Stefanovich, Eugene V.; Boldyrev, Alexander I.; Truong, Thanh N.; Simons, Jack

doi:10.1021/jp980766+

Cited by 59 publications

(59 citation statements)

References 31 publications

(91 reference statements)

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“…Such investigations provide molecular-level information about the solvation of a complex MCA, as well as helping us to understand its properties in electrolyte solutions, on surfaces and at interfaces. Hydration of several common inorganic MCAs has been investigated both experimentally [36] and theoretically [61]. The counterion stabilization of C 2 ¡ 9 by Cs ‡ has also been examined both theoretically and experimentally [62,63].…”

Section: Stabilization Of Mcas In the Gas Phase: From Solvated Clustementioning

confidence: 99%

Probing solution-phase species and chemistry in the gas phase

Wang¹,

Yang²,

Wang³

2002

International Reviews in Physical Chemistry

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Electrospray ionization not only is a powerful soft ionization technique for biological mass spectrometry but also provides an unique interface between the solution phase and the gas phase. An experimental apparatus combining electrospray with photodetachment photoelectron spectroscopy has been developed for the investigation of multiply charged anions and solution-phase species in the gas phase. In this article, the principles of this technique and our recent progress are presented and discussed. Photoelectron spectroscopy is ideal to probe free multiply charged anions and has allowed the repulsive Coulomb barrier existing universally in multiply charged anions to be directly observed and investigated. Solvation e ects, solvent and counter-ion stabilization of a common inorganic doubly charged anion, SO 2 ¡ 4 , have been extensively investigated. The minimum number of water molecules needed to stabilize SO 2 ¡ 4 and its solvation behaviour have been addressed. Large hydrated SO 2 ¡ 4 clusters are found to exhibit properties of bulk aqueous solutions. We also show that the electronic structures of many inorganic metal complexes, in particular redox species, can be investigated in the gas phase using electrospray and photoelectron spectroscopy.

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Section: Stabilization Of Mcas In the Gas Phase: From Solvated Clustementioning

confidence: 99%

Probing solution-phase species and chemistry in the gas phase

Wang¹,

Yang²,

Wang³

2002

International Reviews in Physical Chemistry

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“…5 Atomic radii depending on the molecular context have been used by Olivares del Valle and co-workers, 6 who linked the sizes of the atoms to the Mulliken partial charges; Truong, Nguyen, and Stefanovich have optimized the atomic radii to be used in the GCOSMO model for aqueous solutions. 7 These works have shown that for neutral solutes mean errors with respect to experimental data as low as 0.5 kcal/mol can be obtained with quite a limited number of parameters. The situation is more involved for ionic solutes, where the errors are usually larger than 2 kcal/mol.…”

Section: Introductionmentioning

confidence: 99%

A new definition of cavities for the computation of solvation free energies by the polarizable continuum model

Barone

Cossi

Tomasi

1997

The Journal of Chemical Physics

2,338

1,707

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A set of rules for determining the atomic radii of spheres used to build the molecular cavities in continuum solvation models are presented. The procedure is applied to compute the hydration free energy for molecules containing H, C, N, O, F, P, S, Cl, Br, and I at a computational level ͑Hartree-Fock with a medium size basis set͒ allowing the study of relatively large systems. The optimized radii reduce the mean error with respect to the experimental solvation energies below 0.20 kcal/mol for a set of 43 neutral solutes and around 1 kcal/mol for 27 ions. Moreover the correct trends are observed for the solvation energies of homolog series, like the series ammoniatrimethylamine, that are not correctly reproduced by usual solvation models. © 1997 American Institute of Physics. ͓S0021-9606͑97͒50631-3͔

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“…that is to hold for all surface points s. Similarly, a slight modification [26][27][28][29][30][31][32][33][34][35][36] dubbed the generalized GCOSMO can be operationally defined through…”

Section: Relation To Conductorlike Screening Models Cosmo and Gcosmomentioning

confidence: 99%

“…The formal relation to conductorlike screening models [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] is considered, and it is found that these implicitly include the simulation of volume polarization. This clarifies various findings in the literature that were previously poorly understood.…”

Section: Introductionmentioning

confidence: 99%

Simulation of volume polarization in reaction field theory

Chipman¹

1999

The Journal of Chemical Physics

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Articles you may be interested inHow to measure a complete set of polarization-dependent differential cross sections in a scattering experiment with aligned reagents?In the reaction field theory of solvation, penetration of charge density outside the cavity nominally enclosing the solute leads to a volume polarization that contributes in addition to the commonly recognized surface polarization. In principle the exact volume polarization charge density is spread everywhere outside the cavity, but its effect can be closely and concisely simulated by a certain additional surface polarization charge density. Formal comparison is made to conductorlike screening models, and it is found that these improve on common approaches that neglect volume polarization by automatically including the simulation of volume polarization. A revised method to numerically determine this simulation is also described.

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Ab Initio Study of the Stabilization of Multiply Charged Anions in Water

Cited by 59 publications

References 31 publications

Probing solution-phase species and chemistry in the gas phase

Probing solution-phase species and chemistry in the gas phase

A new definition of cavities for the computation of solvation free energies by the polarizable continuum model

Simulation of volume polarization in reaction field theory

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