Dielectrons in water clusters

Journal Article · Wed Jul 15 04:00:00 EDT 1992 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.463263· OSTI ID:7105538

Kaukonen, H; Barnett, R N; Landman, U ^[1]

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1. School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States)

The energetics, structure, and stability of a dielectron solvated in an internal cavity in water clusters, (H{sub 2}O){sup {minus}2}{sub {ital n}}, at 300 K are investigated using coupled quantum-classical molecular-dynamics simulations. In these calculations the ground state of the dielectron is calculated concurrently with the atomic configurations using the local-spin-density functional method, and the nuclear degrees of freedom evolve classically on the Born--Oppenheimer potential-energy surface. For {ital n}=64 and 128 the internal single-cavity dielectron state is unstable, while for {ital n}=256 (as well as in bulk water) it is energetically stable, fluctuating between a compact spherical configuration ({ital e}{sub 2{ital c}}) and an elongated ellipsoidal dumbbell-shaped one ({ital e}{sub 2{ital d}}). Transitions between these two states of the dielectron are accompanied by structural and orientational transformations of the surrounding water molecules. The induced molecular orientational order is enhanced and is of longer range in (H{sub 2}O){sup {minus}2}{sub 256} than is the case for a solvated single excess electron. By extrapolating our results to the bulk limit we conclude that a spin-paired dielectron state in bulk water, at 300 K, is a stable species relative to two single separated hydrated electrons.

• DOE Contract Number: FG05-86ER45234
• OSTI ID: 7105538
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 97:2; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

664500* -- Special Atoms & Molecules-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
BORN-OPPENHEIMER APPROXIMATION
CLASSICAL MECHANICS
COUPLING
DYNAMICS
ELECTRONS
ELEMENTARY PARTICLES
ENERGY
ENERGY LEVELS
EXTRAPOLATION
FERMIONS
FLUCTUATIONS
GROUND STATES
HYDROGEN COMPOUNDS
LEPTONS
MECHANICS
MOLECULES
NUMERICAL SOLUTION
ORIENTATION
OXYGEN COMPOUNDS
POTENTIAL ENERGY
QUANTUM MECHANICS
SIMULATION
SOLVATED ELECTRONS
STABILITY
STRUCTURE FACTORS
TEMPERATURE RANGE
TEMPERATURE RANGE 0273-0400 K
VARIATIONS
WATER