Quantum simulations and ab initio electronic structure studies of (H sub 2 O) sup minus sub 2

Journal Article · Fri Dec 15 04:00:00 EST 1989 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.457248· OSTI ID:5124747

Barnett, R N; Landman, U ^[1]; Dhar, S; Kestner, N R ^[2]; Jortner, J; Nitzan, A ^[3]

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1. School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332 (US)
2. Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803 (US)
3. School of Chemistry, Sackler Faculty of Exact Science, Tel Aviv University, Tel Aviv 69978, Israel (IS)

The energetics of the negatively charged water dimer (H{sub 2}O){sup {minus}}{sub 2}, is studied using quantum-simulation techniques and {ital ab initio} electronic structure calculations. Using the RWK2-M potentials for water and a pseudopotential for the interaction of an electron with a water molecule in the ground state, consisting of Coulomb, adiabatic polarization, exclusion, and exchange contributions, it was found via the quantum path-integral molecular dynamics and the coupled quantum-classical time-dependent self-consistent field methods that while the minimum energy of (H{sub 2}O){sup {minus}}{sub 2} corresponds to a nuclear configuration similar to that found for the neutral (H{sub 2}O){sub 2} cluster, other nuclear configurations are also exhibited at finite temperature, characterized by a higher total molecular cluster dipole moment and a larger magnitude of the excess electron binding energy. Quantitative agreement is found between the results obtained by the quantum simulations, employing the excess electron--molecule pseudopotential, and those derived, for selected nuclear configurations, via {ital ab initio} calculations, employing the Gaussian 86 code with the basis set for the water molecules supplemented by a large diffuse set located at the midpoint of the two oxygens and in addition by a diffuse set for the excess electron.

• OSTI ID: 5124747
• Journal Information: Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 91:12; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ANIONS
CHARGED PARTICLES
DIMERS
ELECTRONIC STRUCTURE
HYDROGEN COMPOUNDS
IONS
MECHANICS
OXYGEN COMPOUNDS
POTENTIALS
QUANTUM MECHANICS
SELF-CONSISTENT FIELD
SIMULATION
WATER