The OH Radical-H2O Molecular Interaction Potential

Journal Article · Wed Jun 14 04:00:00 EDT 2006 · Journal of Chemical Physics, 124:224318 (15)

DOI:https://doi.org/10.1063/1.2200701· OSTI ID:884824

Du, Shiyu; Francisco, Joseph; Schenter, Gregory K; Iordanov, Tzvetelin D; Garrett, Bruce C; Dupuis, Michel; Li, Jun

The OH radical is one of the most important oxidants in the atmosphere due to its high reactivity. The study of hydrogen-bonded complexes of OH with the water molecules is a topic of significant current interest. In this work, we present the development of a new analytical functional form for the interaction potential between rigid OH radical and H2O molecules. To do this we fit a selected functional form to a set of high level ab initio data. Since there are low-lying excited states for the H2O•OH complex, the impact of the excited states on the chemical behavior of the OH radical can be very important. We perform a Potential Energy Surface (PES) scan using the CCSD(T)/aug-cc-pVTZ level of electronic structure theory for both excited and ground states. To model the physics of the unpaired electron in the OH radical, we develop a tensor polarizability generalization of the Thole Type all-atom polarizable rigid potential for the OH radical, which effectively describes the interaction of OH with H2O for both ground and excited states. The stationary points of (H2O)n•OH clusters were identified as a benchmark of the potential. Battelle operated PNNL for the USDOE.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 884824
• Report Number(s): PNNL-SA-48458; KC0301020
• Journal Information: Journal of Chemical Physics, 124:224318 (15), Journal Name: Journal of Chemical Physics, 124:224318 (15) Vol. 124; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ELECTRONIC STRUCTURE
EXCITED STATES
GROUND STATES
H2O molecules
HYDROXYL RADICALS
INTERACTIONS
OH radical
OXIDIZERS
PES scan
POLARIZABILITY
POTENTIAL ENERGY
WATER
ab initia
hydrogen-bonded complexes
potential energy surface scan