Structures, energetics, and spectra of fluoride–water clusters F−(H2O)n, n=1–6: <i>Ab initio</i> study

Baik, Jiwon; Kim, Jongseob; Majumdar, D.; Kim, Kwang S.

doi:10.1063/1.478833

Cited by 135 publications

(118 citation statements)

References 92 publications

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“…1. To obtain the lowest energy conformers, we have investigated many possible structures of various topologies along with diverse hydration structures of anion-water clusters [21][22][23] and electron-water clusters. 24 The ZPE uncorrected ͑⌬E e ͒ and corrected ͑⌬E 0 ͒ interaction energies for various structures of hydrated hydride anions are listed in Table I.…”

Section: A Structures and Interaction Energiesmentioning

confidence: 99%

Hydrated hydride anion clusters

Lee

Kim²,

Singh³

et al. 2007

The Journal of Chemical Physics

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On the basis of density functional theory ͑DFT͒ and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations ͑based on the Born-Oppenheimer potential surface͒ show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

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Section: A Structures and Interaction Energiesmentioning

confidence: 99%

Hydrated hydride anion clusters

Lee

Kim²,

Singh³

et al. 2007

The Journal of Chemical Physics

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“…It is interesting to consider that in the case of halide microhydration many of the optimized structures have similar energies and the order of stability can change when thermal corrections and zero point vibrational effects are included. 17,19,20,[37][38][39] Thus, it could be unsafe trying to understand the structure of ͓X(H 2 O) n ͔ Ϫ clusters in terms of local minima. In this sense, the analysis of our MC trajectories indicates how different structures with similar interaction energy present different E stab values.…”

Section: Resultsmentioning

confidence: 99%

“…22 Although some authors 17,20,21,24 demonstrate that the use of Koopmans' theorem to compute ionization potentials of bare anions and ͓X(H 2 O) n ͔ Ϫ clusters overestimates the results by 0.4 -0.5 eV, its use to get ionization potential differences is suitable [23][24][25] because almost the same error exists in both systems.…”

Section: Methodsmentioning

confidence: 99%

“…Kim and co-workers [17][18][19][20][21] work, among other properties, on the ab initio prediction of the stabilization energies of ͓X(H 2 O) n ͔ Ϫ clusters (XϵF, Cl, Br, and I, nϭ1 -6) by both calculating the interaction energies difference between the ionic and the neutral cluster and using the Koopmans' theorem. 22 Combariza et al [23][24][25] carry out an ab initio study of the chloride-, bromide-, and iodide-water clusters to establish which are the prevalent isomers in gas phase.…”

Section: Introductionmentioning

confidence: 99%

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Study of the stabilization energies of halide-water clusters: An application of first-principles interaction potentials based on a polarizable and flexible model

Ayala¹,

Martı́nez²,

Pappalardo³

et al. 2004

The Journal of Chemical Physics

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The aim of this work is to compute the stabilization energy E stab (n) of ͓X(H 2 O) n ͔ Ϫ (XϵF, Br, and I for nϭ1 -60) clusters from Monte Carlo simulations using first-principles ab initio potentials. Stabilization energy of ͓X(H 2 O) n ͔ Ϫ clusters is defined as the difference between the vertical photodeachment energy of the cluster and the electron affinity of the isolated halide. On one hand, a study about the relation between cluster structure and the E stab (n) value, as well as the dependence of the latter with temperature is performed, on the other hand, a test on the reliability of our recently developed first-principles halide ion-water interaction potentials is carried out. Two different approximations were applied: ͑1͒ the Koopmans' theorem and ͑2͒ calculation of the difference between the interaction energy of ͓X(H 2 O) n ͔ Ϫ and ͓X(H 2 O) n ͔ clusters using the same ab initio interaction potentials. The developed methodology allows for using the same interaction potentials in the case of the ionic and neutral clusters with the proviso that the charge of the halide anion was switched off in the latter. That is, no specific parametrization of the interaction potentials to fit the magnitude under study was done. The good agreement between our predicted E stab (n) and experimental data allows us to validate the first-principles interaction potentials developed elsewhere and used in this study, and supports the fact that this magnitude is mainly determined by electrostatic factors, which can be described by our interaction potentials. No relation between the value of E stab (n) and the structure of clusters has been found. The diversity of E stab (n) values found for different clusters with similar interaction energy indicates the need for statistical information to properly estimate the stabilization energy of the halide anions. The effect of temperature in the prediction of the E stab (n) is not significant as long as it was high enough to avoid cluster trapping into local equilibrium configurations which guarantees an appropriate sampling of the configurational space. Parallel tempering method was applied in particular cases to guarantee satisfactory sampling of clusters at low temperature.

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“…[71][72][73][74][75][76][77][78][79][80][81][82][83] On the other hand, in the anion water clusters the contribution of electrostatic interactions is less effective because they have a lower ratio of charge to radius than isoelectronic cations, while the polarization effect becomes significant. In anion-water clusters, [84][85][86][87][88][89][90][91][92][93] the anionwater dipole interaction is suppressed, and the inter-water Hbonding interactions around the anion become important. As the hydrogen atoms point toward the anion, there can be strong repulsions between hydrogen atoms.…”

Section: Clustersmentioning

confidence: 99%

Understanding Clusters toward the Design of Functional Molecules and Nanomaterials

Singh

Lee

Choi

et al. 2007

Bulletin of the Chemical Society of Japan

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In this account, we highlight the theoretical investigations of various cluster systems comprising of water clusters, -containing clusters, and metallic clusters. We illustrate how these investigations help us understand and design structures and properties of nanowires, novel functional ionophores/receptors, and nanomaterials. Many of these theoretically predicted systems have been experimentally realized and some of the predicted structures/properties are left for the future which of course could be promising challenges for experimentalists.

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Structures, energetics, and spectra of fluoride–water clusters F−(H2O)n, n=1–6: Ab initio study

Cited by 135 publications

References 92 publications

Hydrated hydride anion clusters

Hydrated hydride anion clusters

Study of the stabilization energies of halide-water clusters: An application of first-principles interaction potentials based on a polarizable and flexible model

Understanding Clusters toward the Design of Functional Molecules and Nanomaterials

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