Dielectron Attachment and Hydrogen Evolution Reaction in Water Clusters

Barnett, R. N.; Giniger, Rina; Cheshnovsky, Ori; Landman, Uzi

doi:10.1021/jp201560n

Cited by 42 publications

(98 citation statements)

References 78 publications

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“…The BOMD technique has been used for adiabatic simulations of excess electrons in finite water clusters. 134,135,136,137,138,139,140 Due to the many electron character of both CPMD and BOMD, they both currently retain serious size limitations. In fact, it remains unclear if CPMD simulations using periodic simulation cells with 32 molecules faithfully represent the bulk hydrated electron system.…”

Section: Ab Initio Molecular Dynamics Techniquesmentioning

confidence: 99%

“…In fact, it remains unclear if CPMD simulations using periodic simulation cells with 32 molecules faithfully represent the bulk hydrated electron system. 131,132 Cluster BOMD studies [134][135][136][137][138][139][140] Most recently, this correction has also been applied in hydrated electron simulations. 136,137,138 The second problem is due to self-interaction energies in DFT calculations in systems with unpaired electrons, necessarily an issue in hydrated electron simulations, in particular with gradient-corrected approximations (such as with BLYP or PBE functionals).…”

Section: Ab Initio Molecular Dynamics Techniquesmentioning

confidence: 99%

“…304 Simulations of transient spectroscopy indicate clear pump-probe signatures that can be used to distinguish between singlet-state hydrated dielectrons and hydrated electrons. 305 The first experimental observation of the hydrated dielectron has been reported in water clusters recently by Barnett et al 140 Water cluster anions were produced by supersonic expansion of water vapor in Ne carrier gas intersected by an electron beam. The time-of-flight mass spectrometer indicated three types of clusters: singly-charged water cluster anions dominate the spectrum, but smaller peaks also appear in the 83 ≤ n < 105 range suggesting the presence of doubly charged water cluster anions, ( ) − 2 2 O H n .…”

Section: The Dynamics and Reactivity Of The Hydrated Dielectronmentioning

confidence: 99%

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Theoretical Studies of Spectroscopy and Dynamics of Hydrated Electrons

2012

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Section: Ab Initio Molecular Dynamics Techniquesmentioning

confidence: 99%

Section: Ab Initio Molecular Dynamics Techniquesmentioning

confidence: 99%

Section: The Dynamics and Reactivity Of The Hydrated Dielectronmentioning

confidence: 99%

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Theoretical Studies of Spectroscopy and Dynamics of Hydrated Electrons

2012

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“…3,4,5,6,7 The VDE-size diagrams exhibit various systematic patterns that may indicate common structural motifs within the groups. Based on early 8 and subsequent improved one-electron model quantum simulations, 9,10 and an allelectron density functional theory based molecular dynamics study, 11 tentative assignments of the different anionic groups have been proposed. Unfortunately, these theoretical predictions do not necessarily match the experimentally inferred classifications.…”

Section: Introductionmentioning

confidence: 99%

On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

Túri

2016

The Journal of Chemical Physics

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We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with 1 E-mail: turi@chem.elte.hu, fax: (36)-1-372-2592.3 precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations that represent possible excess electron binding motifs in the clusters appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model. 4

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“…21,22,23 Many electron ab initio molecular dynamics (AIMD) simulations, that are becoming gradually the choice of the method, are aimed at the more precise characterization of the system. 13,24,25,26,27,28,29 Problems of AIMD, however, still persist in terms of the selection of the electronic structure calculation method, the simulated system size, and the sampling efficiency. These limitations of AIMD equally contribute to the fact that QCMD methods are still widely applied, even though these latter methods can be viewed realistically as semi-quantitative.…”

Section: Introductionmentioning

confidence: 99%

Hydrated Electrons in Water Clusters: Inside or Outside, Cavity or Noncavity?

Túri

2015

J. Chem. Theory Comput.

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We compare the applicability of three electron-water molecule pseudopotential models in modeling hydrated electron physical properties. The analysis is based on a) simple quantum mechanical model calculations, and b) one-electron mixed quantum-classical molecular dynamics simulations of an excess electron in size selected water cluster anions. The quantum mechanical calculations illustrate that the recently suggested Larsen-Glover-Schwartz (LGS) model predicts a too attractive potential in the vicinity of the oxygen. As a result, the LGS ground state eigenvalue and the asymptotic behavior of the model wave function are inaccurate. The TuriBorgis (TB) potential used for comparative purposes reproduces these properties satisfactorily.Mixed quantum-classical molecular dynamics simulations on negatively charged water clusters provide an ideal test case for further testing the potentials. In addition to the LGS and TB models, we also investigated a modified form of the LGS model (m-LGS) that were introduced to correct the huge overbinding of the electron in bulk LGS simulations. While the LGS and m-LGS 1 E-mail: turi@chem.elte.hu, fax: (36)-1-372-2592. 3 models predict non-cavity hydrated electron structure in clusters at room temperature, the TB potential prefers the traditionally accepted cavity structure. As another major difference, the electron exclusively localizes in the interior of the clusters in LGS based simulations, while two possible isomers (interior vs. surface state isomers) emerge from TB calculations. The computed associated physical properties are also analyzed and compared to available experimental data. We found that the LGS and m-LGS potentials provide results that are inconsistent with the size dependence of the experimental data. In particular, LGS simulations fail to reproduce the trends of the radius of the excess electron and the position of the absorption spectra with cluster size.The simulated TB tendencies are qualitatively correct. In conclusion, we observe that the cavity preferring pseudopotential model results physical properties in significantly better agreement with experimental data than the models predicting non-cavity structure for the hydrated electron.

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Dielectron Attachment and Hydrogen Evolution Reaction in Water Clusters

Cited by 42 publications

References 78 publications

Theoretical Studies of Spectroscopy and Dynamics of Hydrated Electrons

Theoretical Studies of Spectroscopy and Dynamics of Hydrated Electrons

On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

Hydrated Electrons in Water Clusters: Inside or Outside, Cavity or Noncavity?

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