Title: Ab initio potential energy surface for the nitrogen molecule pair and thermophysical properties of nitrogen gas
Authors: Hellmann, Robert 
Language: eng
Keywords: Ab initio calculations;Kinetic theory;Nitrogen pair potential;Transport properties;Virial coefficients
Issue Date: 1-Feb-2013
Document Type: Article
Journal / Series / Working Paper (HSU): Molecular Physics
Volume: 111
Issue: 3
Page Start: 387
Page End: 401
A four-dimensional potential energy hypersurface (PES) for the interaction of two rigid nitrogen molecules was determined from high-level quantum-chemical ab initio computations. A total of 408 points for 26 distinct angular configurations were calculated utilizing the counterpoise-corrected supermolecular approach at the CCSD(T) level of theory and basis sets up to aug-cc-pV5Z supplemented with bond functions. The calculated interaction energies were extrapolated to the complete basis set limit and complemented by corrections for core-core and core-valence correlations, relativistic effects and higher coupled-cluster levels up to CCSDT(Q). An analytical site-site potential function with five sites per nitrogen molecule was fitted to the interaction energies. The PES was validated by computing second and third pressure virial coefficients as well as shear viscosity and thermal conductivity in the dilute-gas limit. An improved PES was obtained by scaling the CCSDT(Q) corrections for all 408 points by a constant factor, leading to quantitative agreement with the most accurate experimental values of the second virial coefficient over a wide temperature range. The comparison with the best experimental data for shear viscosity shows that the values computed with the improved PES are too low by about 0.3% between 300 and 700 K. For thermal conductivity large systematic deviations are found above 500 K between the calculated values and most of the experimental data. © 2013 Copyright Taylor and Francis Group, LLC.
Organization Units (connected with the publication): Universität Rostock
ISSN: 00268976
Publisher DOI: 10.1080/00268976.2012.726379
Appears in Collections:6 - Bibliographic Data - Publications of the HSU Researchers (before HSU)

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