Small Multiply Charged Anions as Building Blocks in Chemistry

Boldyrev, Alexander I.; Gutowski, Maciej; Simons, Jack

doi:10.1021/ar960147o

Cited by 175 publications

(193 citation statements)

References 53 publications

(59 reference statements)

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“…The internuclear distances of doubly charged CO 3 2-and SO 4 2-(see Table 1) in water are very close to those in the isolated state, although the latter are electronically unstable. Specifically, the C-O and S-O bonds shrink by about 0.01 Å when solvated.…”

Section: A Effect Of Water On the Geometry Of Multiply Chargedmentioning

confidence: 68%

“…We optimized the geometries of the isolated CO 3 2-, SO 4 2-, and PO 4 3-species employing analytical gradients with polarized split-valence basis sets (6-311+G*) at the MP2(full) level of theory. For calculations on MgF 2 , MgF 3 -, MgF 4 2-, MgF 5 3-, and MgF 6 4-we used 6-31+G* basis sets and nonlocal density functional B3LYP levels of theory.…”

Section: Methodsmentioning

confidence: 99%

“…), many of which are commonly viewed as building blocks in the condensed phase, are not electronically stable as isolated species. [3][4][5][6][7][8][9] When multiply charged anions are placed into a condensedphase environment, such as in aqueous solution, a substantial enhancement of both the electronic and thermodynamic stabilities can occur due to the solvent polarization field, which lowers the free energy of the charged solutes in a manner approximately proportional to the anion's charge squared. Although the effects of ion stabilization in polar media are qualitatively understood, the magnitudes of these effects are the subject of active investigations.…”

Section: Introductionmentioning

confidence: 99%

“…All but MgF 4 2-were previously found to be electronically unstable in the isolated state. [3][4][5][6][7][8][9] 3. How large is the effect of the water on the thermodynamic stability of multiply charged anions?…”

Section: Introductionmentioning

confidence: 99%

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

Stefanovich¹,

Boldyrev²,

Truong³

et al. 1998

J. Phys. Chem. B

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Solvation effects on the geometries and electronic and thermodynamic stabilities of a series of small multiply charged polyatomic anions, which are not electronically and thermodynamically stable in the isolated state, have been studied using the generalized conductor-like screening model of solvation. It was found that small doubly charged anions such as O 2-, CO 3 2-, and SO 4 2-are electronically very stable in water with estimated vertical electron detachment energies as high as 6-7 eV. Even the triply charged (BO 4-are not stable toward loss of one F -anion, but the doubly and triply charged anions were found to be thermodynamically stable in water. Surprisingly, the aqueous electron detachment energies are not very strongly dependent on the charge of the anion, and the thermodynamic stabilities of singly, doubly, and triply charged MgF (2+n) n-anions are very similar (as a result of which one can expect the coexistence of various charged anions in solutions and in melts).

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Section: A Effect Of Water On the Geometry Of Multiply Chargedmentioning

confidence: 68%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Stefanovich¹,

Boldyrev²,

Truong³

et al. 1998

J. Phys. Chem. B

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“…[75][76][77][78][79][80] The coupling of ESI with PES allowed MCAs to be spectroscopically characterized for the first time. [4][5][6][32][33][34][35][36][37][38][39][40] When an electron is detached from a MCA, it experiences a short-range attraction by the nuclei and a long-range repulsion from the negatively charged residual ion, resulting in the socalled RCB (Fig.…”

Section: Photoelectron Imaging Of Multiply-charged Anions: the Imentioning

confidence: 99%

A multi-agent quantum Monte Carlo model for charge transport: Application to organic field-effect transistors

Bauer

Jäger

Jordan

et al. 2015

The Journal of Chemical Physics

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We have developed a multi-agent quantum Monte Carlo model to describe the spatial dynamics of multiple majority charge carriers during conduction of electric current in the channel of organic field-effect transistors. The charge carriers are treated by a neglect of diatomic differential overlap Hamiltonian using a lattice of hydrogen-like basis functions. The local ionization energy and local electron affinity defined previously map the bulk structure of the transistor channel to external potentials for the simulations of electron- and hole-conduction, respectively. The model is designed without a specific charge-transport mechanism like hopping- or band-transport in mind and does not arbitrarily localize charge. An electrode model allows dynamic injection and depletion of charge carriers according to source-drain voltage. The field-effect is modeled by using the source-gate voltage in a Metropolis-like acceptance criterion. Although the current cannot be calculated because the simulations have no time axis, using the number of Monte Carlo moves as pseudo-time gives results that resemble experimental I/V curves.

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Favorable performance of the DFT methods in predicting the minimum-energy structure of the lowest triplet state of WF4

Gutowski

1999

Int. J. Quant. Chem.

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ABSTRACT:The tetrahedral structure of the lowest triplet state of the WF complex 4 Ž . was examined using different variants of the density functional theory DFT and conventional ab initio methods. The low-level, conventional, ab initio methods, such as SCF, MP2, MP3, and CISD, predict the tetrahedral structure to be a minimum, whereas the DFT schemes predict an imaginary frequency for the e vibrational mode. Only after recovering electron correlation effects at the MP4 and higher levels, the conventional electronic structure methods also predict the T structure to be a second-order stationary d point. This is not the correlation but the exchange part of the DFT functionals which is responsible for the discrepancy between the DFT and low-level, conventional, ab initio predictions. The lowering of symmetry to C leads to a minimum on the lowest triplet Ž . stationary points amounts to 0.85 and 0.96 kcalrmol at the B3LYP and CCSD T levels, respectively.

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Small Multiply Charged Anions as Building Blocks in Chemistry

Cited by 175 publications

References 53 publications

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

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

A multi-agent quantum Monte Carlo model for charge transport: Application to organic field-effect transistors

Favorable performance of the DFT methods in predicting the minimum-energy structure of the lowest triplet state of WF4

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