Methane high-temperature partition function from contact transformations and variational calculations. (December 2015)

• Record Type: Journal Article
• Authors: Nikitin, A.V.; Krishna, B.M.; Rey, M.; Tashkun, S.A.; Tyuterev, VI.G.
• Is Part Of: Journal of quantitative spectroscopy & radiative transfer. Volume 167(2016:May)
• Page Start: 53
• Page End: 63
• Publication Date: 2015-12
• Subjects: Near infrared methane -- Hot bands -- Partition function -- Outer planets; Spectrum analysis -- Periodicals; Radiation -- Periodicals; Analyse spectrale -- Périodiques; Rayonnement -- Périodiques; Radiation; Spectrum analysis; Periodicals; 543.0858
• DOI: 10.1016/j.jqsrt.2015.08.004
• Languages: English
• ISSNs: 0022-4073

Abstract

Abstract: The temperature dependence of the methane 12 CH4 partition function was investigated up to T =3000 K. The ro-vibrational energy levels were calculated using high-order contact transformation (CT) method that permitted building accurate effective Hamiltonian models for highly excited vibration–rotation states from the molecular potential energy surface. Comparisons with variational calculations using large basis sets as well as convergence and extrapolation issues are discussed. The accuracy of the present calculations for the methane partition function was estimated as 1–2% at 2000 K. This estimated error is considerably smaller than the difference with other calculations available in the literature. Highlights: Methane partition function was calculated up to 3000 K. Comparison of contact transformation and variational methods is discussed. Contributions from high polyads are evaluated.