Interior- and surface-bound excess electron states in large water cluster anions

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

doi:doi:10.1063/1.3094732

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Photoinduced quantum dynamics of ortho- and para-fulvene: Hindered photoisomerization due to mode selective fast radiationless decay via a conical intersection

In this study, we investigate the photoinduced nonadiabatic dynamics of para- and ortho-fulvene by a combination of quantum chemical ab initio calculations and quantum dynamical simulations. We explore the competition between two different pathways, the photoisomerization and radiationless decay via a conical intersection (CI) at planar configuration. For this purpose, we extend a previous two-dimensional model which included the molecular torsion and the antisymmetric stretch as a coupling mod...

Bond breaking in light-induced potentials

We study the photodissociation of ICl− under moderately strong (TW/cm2) and short (below picosecond) laser pulses. Using a single resonant pump pulse, the photodissociation spectra shows two barely overlapping bands corresponding to Frank–Condon excitation and dissociation in two electronic states. By adding a nonresonant stronger control pulse we show that (1) the photodissociation bands can be blueshifted and (2) the asymptotic state of the fragments depends on the chosen pulse sequence. If t...

We present the results of mixed quantum/classical simulations on relaxed thermal nanoscale water cluster anions, (H₂O)n−, with n = 200, 500, 1000, and 8000. By using initial equilibration with constraints, we investigate stable/metastable negatively charged water clusters with both surface-bound and interior-bound excess electron states. Characterization of these states is performed in terms of geometrical parameters, energetics, and optical absorption spectroscopy of the clusters. The calculations provide data characterizing these states in the gap between previously published calculations and experiments on smaller clusters and the limiting cases of either an excess electron in bulk water or an excess electron at an infinite water/air interface. The present results are in general agreement with previous simulations and provide a consistent picture of the evolution of the physical properties of water cluster anions with size over the entire size range, including results for vertical detachment energies and absorption spectra that would signify their presence. In particular, the difference in size dependence between surface-bound and interior-bound state absorption spectra is dramatic, while for detachment energies the dependence is qualitatively the same.

Article Outline

INTRODUCTION
METHODS
RESULTS
DISCUSSION AND CONCLUSIONS

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KEYWORDS and PACS

Keywords

infrared spectra, molecular clusters, negative ions, ultraviolet spectra, visible spectra, water

PACS

36.40.Cg

Electronic and magnetic properties of clusters
36.40.Mr

Spectroscopy and geometrical structure of clusters
36.40.Wa

Charged clusters
33.20.Kf

Visible spectra
33.20.Ea

Infrared spectra
33.20.Lg

Ultraviolet spectra

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.3094732

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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