Photoelectron spectra of the hydrated iodine anion from molecular dynamics simulations

Journal Article · Sun Aug 15 00:00:00 EDT 1993 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.465203· OSTI ID:6172349

Dang, L X; Garrett, B C ^[1]

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1. Molecular Science Research Center, Pacific Northwest Laboratory, Richland, Washington 99352 (United States)

In this paper, we present the first calculations, based on molecular dynamics techniques, of vertical electron binding energies for the ionic clusters I[sup [minus]](H[sub 2]O)[sub [ital n]], ([ital n]=1--15). In these studies, we employ the polarizable water model developed recently by Dang [J. Chem. Phys. [bold 97], 2659 (1992)]. We construct the ion--water potential so that the successive binding energies for the ionic clusters, the hydration enthalpy, and the structural properties of the aqueous ionic solution agree with the results obtained from experiments. The simulated vertical electron binding energies compare well with recent data from photoelectron spectroscopy experiments by Markovich, Giniger, Levin, and Cheshnovsky [J. Chem. Phys. [bold 95], 9416 (1991)]. Interestingly, we obtain coordination numbers of 4 to 5 for the ionic clusters, I[sup [minus]](H[sub 2]O)[sub [ital n]], for [ital n][ge]6. This result is smaller than the coordination number, based on the energetic properties predicted by Markovich [ital et] [ital al]. Possible reasons for this discrepancy are discussed in the paper. Furthermore, our simulations place the iodine anion on the surface of the water clusters. This study demonstrates the usefulness of the molecular dynamics technique and provides a detailed picture of the ion solvation in clusters.

• DOE Contract Number: AC06-76RL01830
• OSTI ID: 6172349
• Journal Information: Journal of Chemical Physics; (United States), Vol. 99:4; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
74 ATOMIC AND MOLECULAR PHYSICS
IODINE IONS
BINDING ENERGY
ION PAIRS
WATER
ANIONS
AQUEOUS SOLUTIONS
FORMATION FREE ENTHALPY
HYDRATION
PHOTOELECTRON SPECTROSCOPY
POLARIZABILITY
POTENTIALS
SIMULATION
STRUCTURE FACTORS
CHARGED PARTICLES
DISPERSIONS
ELECTRICAL PROPERTIES
ELECTRON SPECTROSCOPY
ENERGY
FREE ENTHALPY
HYDROGEN COMPOUNDS
IONS
MIXTURES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
SOLUTIONS
SOLVATION
SPECTROSCOPY
THERMODYNAMIC PROPERTIES
665000* - Physics of Condensed Matter- (1992-)
664500 - Special Atoms & Molecules- (1992-)