Water Dimers in the Atmosphere II: Results from the VRT(ASP-W)III Potential Surface

Journal Article · Wed Oct 01 04:00:00 EDT 2003 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

OSTI ID:15014362

Goldman, N; Saykally, R J; Leforestier, C

We report refined results for the equilibrium constant for water dimerization (K{sub P}), computed as a function of temperature via fully-coupled 6-D calculation of the canonical (H{sub 2}O){sub 2} partition function on VRT(ASP-W)III, the most accurate water dimer potential energy surface currently available. Partial pressure isotherms calculated for a range of temperatures and relative humidities indicate that water dimers can exist in sufficient concentrations (e.g., 10{sup 18}m{sup -3} at 30 C and 100% relative humidity) to affect physical and chemical processes in the atmosphere. The determinations of additional thermodynamic properties ({Delta}G, {Delta}H, {Delta}S, C{sub P}, C{sub V}) for (H{sub 2}O){sub 2} are presented, and the role of quasi-bound states in the calculation of K{sub P} is discussed at length.

• Research Organization: Lawrence Livermore National Laboratory (LLNL), Livermore, CA
• Sponsoring Organization: USDOE
• DOE Contract Number: W-7405-ENG-48
• OSTI ID: 15014362
• Report Number(s): UCRL-JRNL-200119
• Journal Information: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 5 Vol. 108; ISSN 1089-5639; ISSN JPCAFH
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DIMERS
PARTIAL PRESSURE
PARTITION FUNCTIONS
POTENTIAL ENERGY
THERMODYNAMIC PROPERTIES
WATER