The Gas and Solution Phase Acidities of HNO, HOONO, HONO, and HONO2

Journal Article · Tue Jul 01 04:00:00 EDT 2003 · International Journal of Mass Spectrometry

DOI:https://doi.org/10.1016/S1387-3806(03)00095-2· OSTI ID:15015218

Dixon, David A; Feller, David F; Zhan, Chang-Guo; Francisco, Joseph S

The acidities of HNO{sub x} (where x = 1-3) have been calculated in the gas phase and in solution by using high level ab initio molecular orbital theory. Coupled cluster (CCSD(T)) energies, extrapolated to the complete basis set (CBS) limit, were used to determine thermodynamic properties of the species in the gas phase, and the fully polarizable continuum model (FPCM) was used to calculate the effect of solvent on the energy changes. The calculated gas phase heats of formation in kcal/mol at 0 K of the neutral compounds, based on extrapolations through the aug-cc-pVQZ basis set, are: {Delta}H{sub f}(NO) = 22.07 (calc.) vs. 21.46 {+-} 0.04(expt.); {Delta}H{sub f}(HNO) = 26.39 (calc.) vs. 26.3 {+-} 1 (expt.); {Delta}H{sub f}(NO{sub 2}) = 10.12 (calc.) vs. 8.59 {+-} 0.2(expt.); {Delta}H{sub f}f(HONO{sub 2}) = -29.87 (calc.) vs. -29.75 {+-} 0.1(expt.); {Delta}H{sub f}(HONO) = -15.79 (calc.) vs. -17.37 {+-} 0.32 (expt.); {Delta}H{sub f}(HOONO) = -0.89 (calc.); {Delta}H{sub f}(NO{sub 2}{sup -}) = -41.95 (calc.) vs. -43.8 {+-} 0.2(expt.); {Delta}H{sub f}(NO{sub 3}{sup -}) = -70.76 (calc.) vs. -71.7 {+-} 0.30(expt.); and {Delta}H{sub f}(ONOO{sup -}) = -16.74 (calc.). The electron affinity of NO is calculated to be 0.62 kcal/mol, based on extrapolations up through the aug-cc-pV5Z basis set, and falls within 0.02 kcal/mol of the experimental value.

• Research Organization: Pacific Northwest National Lab., Richland, WA (US), Environmental Molecular Sciences Laboratory (US)
• Sponsoring Organization: US Department of Energy (US)
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 15015218
• Report Number(s): PNNL-SA-41158; 3565; KC0301020
• Journal Information: International Journal of Mass Spectrometry, Journal Name: International Journal of Mass Spectrometry Journal Issue: 3 Vol. 227
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
AFFINITY
ENVIRONMENTAL MOLECULAR SCIENCES LABORATORY
MOLECULAR ORBITAL METHOD
NITROGEN COMPOUNDS
NITROUS ACID
OXYGEN COMPOUNDS
PH VALUE
PHASE STUDIES
SOLVENTS
THERMODYNAMIC PROPERTIES