Excess electron localization sites in neutral water clusters

Turi, László; Madarász, Ádám; Rossky, Peter J.

doi:doi:10.1063/1.2213965

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Termolecular kinetics for the Mu+CO+M recombination reaction: A unique test of quantum rate theory

The room-temperature termolecular rate constants, k0, for the Mu+CO+M⇌MuCO+M (M = He, N2, Ar) recombination reaction have been measured by the μSR technique, and are reported for moderator gas pressures of up to ∼ 200 bar (densities ≲0.4×1022 molec cm−3). The experimental relaxation rates reveal an unusual signature, in being dominated by the electron spin-rotation interaction in the MuCO∙ radical that is formed in the addition step. In N2 moderator, k0 = 1.2±0.1×10−34 cm6 s−1, only about 30% ...

Pulsed-field ionization electron spectroscopy and ab initio calculations of copper-diazine complexes

Copper complexes of pyrazine (1,4-C4H4N2), pyrimidine (1,3-C4H4N2), and pyridazine (1,2-C4H4N2) are produced in laser-vaporization supersonic molecular beams and studied by pulsed-field ionization zero electron kinetic energy (ZEKE) spectroscopy and second-order Møller-Plesset perturbation theory. Both σ and π complexes are considered by these ab initio calculations; only σ structures are identified in these experiments. Adiabatic ionization energies and metal-ligand vibrational frequencies of ...

We present approximate pseudopotential quantum-mechanical calculations of the excess electron states of equilibrated neutral water clusters sampled by classical molecular dynamics simulations. The internal energy of the clusters are representative of those present at temperatures of 200 and 300 K. Correlated electronic structure calculations are used to validate the pseudopotential for this purpose. We find that the neutral clusters support localized, bound excess electron ground states in about 50% of the configurations for the smallest cluster size studied (n = 20), and in almost all configurations for larger clusters (n>66). The state is always exterior to the molecular frame, forming typically a diffuse surface state. Both cluster size and temperature dependence of energetic and structural properties of the clusters and the electron distribution are explored. We show that the stabilization of the electron is strongly correlated with the preexisting instantaneous dipole moment of the neutral clusters, and its ground state energy is reflected in the electronic radius. The findings are consistent with electron attachment via an initial surface state. The hypothetical spectral dynamics following such attachment is also discussed.

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INTRODUCTION
METHODS
RESULTS
DISCUSSION AND CONCLUSIONS

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KEYWORDS and PACS

Keywords

water, pseudopotential methods, molecular dynamics method, surface states, localised states, ground states, liquid structure

PACS

61.20.Ja

Computer simulation of liquid structure
71.15.Dx

Computational methodology (Brillouin zone sampling, iterative diagonalization, pseudopotential construction)
61.25.Em

Molecular liquids
73.20.At

Surface states, band structure, electron density of states

ARTICLE DATA

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http://dx.doi.org/10.1063/1.2213965

PUBLICATION DATA

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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