Theoretical studies of electron transfer in metal dimers: XY+→X+Y, where X, Y=Be, Mg, Ca, Zn, Cd

Cave, Robert J.; Baxter, David V.; Goddard, William A.; Baldeschwieler, John D.

doi:10.1063/1.453247

Cited by 54 publications

(33 citation statements)

References 26 publications

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“…, in line with the recently reported value of 2.1 À1 estimated with the INDO Hamiltonian for cofacial pentacene molecules, [36] or with previous ab initio calculations on pentacene dimers [37] and is quite large, as expected for a through-space charge transfer between nonbonded molecules. The electron-transfer rate constant can be described by employing the semiclassical Marcus expression [Eq.…”

supporting

confidence: 86%

Molecular Size and Electronic Structure Combined Effects on the Electrogenerated Chemiluminescence of Sulfurated Pyrene‐Cored Dendrimers

Valenti

Fiorani

Motta

et al. 2014

Chemistry A European J

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The electrochemistry, photophysics, and electrochemically generated chemiluminescence (ECL) of a family of polysulfurated dendrimers with a pyrene core have been thoroughly investigated and complemented by theoretical calculations. The redox and luminescence properties of dendrimers are dependent on the generation number. From low to higher generation it is both easier to reduce and oxidize them and the emission efficiency increases along the family, with respect to the polysulfurated pyrene core. The analysis of such data evidences that the formation of the singlet excited state by cation-anion annihilation is an energy-deficient process and, thus, the ECL has been justified through the triplet-triplet annihilation pathway. The study of the dynamics of the ECL emission was achieved both experimentally and theoretically by molecular mechanics and quantum chemical calculations. It has allowed rationalization of a possible mechanism and the experimental dependence of the transient ECL on the dendrimer generation. The theoretically calculated Marcus electron-transfer rate constant compares very well with that obtained by the finite element simulation of the whole ECL mechanism. This highlights the role played by the thioether dendrons in modulating the redox and photophysical properties, responsible for the occurrence and dynamics of the electron transfer involved in the ECL. Thus, the combination of experimental and computational results allows understanding of the dendrimer size dependence of the ECL transient signal as a result of factors affecting the annihilation electron transfer.

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supporting

confidence: 86%

Molecular Size and Electronic Structure Combined Effects on the Electrogenerated Chemiluminescence of Sulfurated Pyrene‐Cored Dendrimers

Valenti

Fiorani

Motta

et al. 2014

Chemistry A European J

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“…in which J is H(HOMO) or L(LUMO) and with α /2=1.6 Å −1 , in line with the recently reported value of 2.1 Å −1 estimated with the INDO Hamiltonian for cofacial pentacene molecules,36 or with previous ab initio calculations on pentacene dimers37 and is quite large, as expected for a through‐space charge transfer between nonbonded molecules.…”

Section: Methodssupporting

confidence: 90%

Preparation and Hydrogen Sorption Performances of BCNO Porous Microbelts with Ultra‐Narrow and Tunable Pore Widths

Weng

Wang

et al. 2013

Chemistry An Asian Journal

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That′s below the belt: Porous BCNO materials with tunable ultra‐narrow pore widths (0.4–1.1 nm) were prepared and investigated with regard to H2 storage. The as‐prepared samples show similar belt‐like morphologies, chemical compositions, surface areas, and pore volumes. The difference in H2 sorption behavior for the materials reveals that a narrower pore width likely favors H2 uptake at a low pressure range, while an increased proportion of BN domains in the materials may be beneficial to enhance H2 uptake at elevated pressures at 77 K.

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“…They are particularly simple from an electronic structural viewpoint, but Zn 2 ϩ has been well studied in the absence of solvent [37][38][39] in the ground and several low-lying excited states so that the effects of the solvents used here can be accurately assessed. Li 2 ϩ is an extremely simple system, which, when compared with Zn 2 ϩ , allows one to examine the sensitivity of solvent effects to the energy of the donor or acceptor states involved in the process.…”

Section: Introductionmentioning

confidence: 99%

An ab initio study of specific solvent effects on the electronic coupling element in electron transfer reactions

Henderson¹,

Cave²

1998

The Journal of Chemical Physics

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Specific solvent effects on the electronic coupling element for electron transfer are examined using two model donor-acceptor systems (Zn 2 ϩ and Li 2 ϩ ) and several model ''solvent'' species (He, Ne, H 2 O, and NH 3 ). The effects are evaluated relative to the given donor-acceptor pair without solvent present. The electronic coupling element (H ab ) is found to depend strongly on the identity of the intervening solvent, with He atoms decreasing H ab , whereas H 2 O and NH 3 significantly increase H ab . The distance dependence ͑essentially exponential decay͒ is weakly affected by a single intervening solvent atom-molecule. However, when the donor-acceptor distance increases in concert with addition of successively greater numbers of solvent species, the decay with distance of H ab is altered appreciably. Effects due to varying the orientation of molecular solvent are found, somewhat surprisingly, to be quite modest.

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Theoretical studies of electron transfer in metal dimers: XY+→X+Y, where X, Y=Be, Mg, Ca, Zn, Cd

Cited by 54 publications

References 26 publications

Molecular Size and Electronic Structure Combined Effects on the Electrogenerated Chemiluminescence of Sulfurated Pyrene‐Cored Dendrimers

Molecular Size and Electronic Structure Combined Effects on the Electrogenerated Chemiluminescence of Sulfurated Pyrene‐Cored Dendrimers

Preparation and Hydrogen Sorption Performances of BCNO Porous Microbelts with Ultra‐Narrow and Tunable Pore Widths

An ab initio study of specific solvent effects on the electronic coupling element in electron transfer reactions

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