Photoelectron spectra of the hydrated iodine anion from molecular dynamics simulations

Journal Article · Sun Aug 15 04:00:00 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), Journal Name: Journal of Chemical Physics; (United States) Vol. 99:4; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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