title: Modeling Nitrogen Species as Pollutants: Thermochemical Influences.
abstract: To simulate emissions of nitrogen-containing compounds in practical combustion environments, it is necessary to have accurate values for their thermochemical parameters, as well as accurate kinetic values to describe the rates of their formation and decomposition. Significant disparity is observed in the literature for the former, and we therefore present herein high-accuracy ab initio gas-phase thermochemistry for 60 nitrogenous compounds, many of which are important in the formation and consumption chemistry of NOx species. Several quantum-chemical composite methods (CBS-APNO, G3, and G4) were utilized to derive enthalpies of formation via the atomization method. Entropies and heat capacities were calculated from traditional statistical thermodynamics, with oscillators treated as anharmonic based on ro-vibrational property analyses carried out at the B3LYP/cc-pVTZ level of theory. The use of quantum chemical methods, along with the treatments of anharmonicities and hindered rotors, ensures accurate enthalpy of formation, entropy, and heat capacity values across the temperature range 298.15-3000 K. The implications of these results for atmospheric and combustion modeling are discussed.
authors.affiliation: Combustion Chemistry Centre, National University of Ireland , Galway H91 TK33, Ireland.
authors.forename: John
authors.initials: J
authors.lastname: Bugler
authors.affiliation: Combustion Chemistry Centre, National University of Ireland , Galway H91 TK33, Ireland.
authors.forename: Kieran P
authors.initials: KP
authors.lastname: Somers
authors.affiliation: Combustion Chemistry Centre, National University of Ireland , Galway H91 TK33, Ireland.
authors.forename: John M
authors.initials: JM
authors.lastname: Simmie
authors.affiliation: GE Power - GSTRB , Brown Boveri Strasse 7, 5401 Baden, Switzerland.
authors.forename: Felix
authors.initials: F
authors.lastname: Güthe
authors.affiliation: Combustion Chemistry Centre, National University of Ireland , Galway H91 TK33, Ireland.
authors.forename: Henry J
authors.initials: HJ
authors.lastname: Curran
mesh_terms: D019277:Entropy; D004785:Environmental Pollutants / Q000737:chemistry*; D008956:Models, Chemical; D017672:Nitrogen Compounds / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D004785:Environmental Pollutants; D017672:Nitrogen Compounds