First-principles binary diffusion coefficients for H, H2 and four normal alkanes + N2

Jasper, Ahren W.; Kamarchik, Eugene; Miller, James A.; Klippenstein, Stephen J.

doi:10.1063/1.4896368

First-principles binary diffusion coefficients for H, H₂ and four normal alkanes + N₂

Journal Article · Tue Sep 30 00:00:00 EDT 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4896368· OSTI ID:1237364

Jasper, Ahren W. ^[1]; Kamarchik, Eugene ^[1]; Miller, James A. ^[2]; Klippenstein, Stephen J. ^[2]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Collision integrals related to binary (dilute gas) diffusion are calculated classically for six species colliding with N₂. The most detailed calculations make no assumptions regarding the complexity of the potential energy surface, and the resulting classical collision integrals are in excellent agreement with previous semiclassical results for H + N₂ and H₂ + N₂ and with recent experimental results for C _n H_2n+2 + N₂, n = 2–4. The detailed classical results are used to test the accuracy of three simplifying assumptions typically made when calculating collision integrals: (1) approximating the intermolecular potential as isotropic, (2) neglecting the internal structure of the colliders (i.e., neglecting inelasticity), and (3) employing unphysical R^–12 repulsive interactions. The effect of anisotropy is found to be negligible for H + N₂ and H₂ + N₂ (in agreement with previous quantum mechanical and semiclassical results for systems involving atomic and diatomic species) but is more significant for larger species at low temperatures. For example, the neglect of anisotropy decreases the diffusion coefficient for butane + N₂ by 15% at 300 K. The neglect of inelasticity, in contrast, introduces only very small errors. Approximating the repulsive wall as an unphysical R^–12 interaction is a significant source of error at all temperatures for the weakly interacting systems H + N₂ and H₂ + N₂, with errors as large as 40%. For the normal alkanes in N₂, which feature stronger interactions, the 12/6 Lennard–Jones approximation is found to be accurate, particularly at temperatures above –700 K where it predicts the full-dimensional result to within 5% (although with somewhat different temperature dependence). Overall, the typical practical approach of assuming isotropic 12/6 Lennard–Jones interactions is confirmed to be suitable for combustion applications except for weakly interacting systems, such as H + N₂. For these systems, anisotropy and inelasticity can safely be neglected but a more detailed description of the repulsive wall is required for quantitative predictions. Moreover, a straightforward approach for calculating effective isotropic potentials with realistic repulsive walls is described. An analytic expression for the calculated diffusion coefficient for H + N₂ is presented and is estimated to have a 2-sigma error bar of only 0.7%.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1237364

Alternate ID(s):: OSTI ID: 22308237

Report Number(s):: SAND--2015-0160J; 560415

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 12 Vol. 141; ISSN JCPSA6; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (28)

A first-principle calculation of the binary diffusion coefficients pertinent to kinetic modeling of hydrogen/oxygen/helium flames Middha, Prankul; Yang, Benhui; Wang, Hai Proceedings of the Combustion Institute, Vol. 29, Issue 1 https://doi.org/10.1016/S1540-7489(02)80167-5	journal	January 2002
Hydrocarbon binary diffusion coefficient measurements for use in combustion modeling McGivern, W. Sean; Manion, Jeffrey A. Combustion and Flame, Vol. 159, Issue 10 https://doi.org/10.1016/j.combustflame.2012.04.015	journal	October 2012
Lennard–Jones parameters for combustion and chemical kinetics modeling from full-dimensional intermolecular potentials Jasper, Ahren W.; Miller, James A. Combustion and Flame, Vol. 161, Issue 1 https://doi.org/10.1016/j.combustflame.2013.08.004	journal	January 2014
Transport properties for combustion modeling Brown, Nancy J.; Bastien, Lucas A. J.; Price, Phillip N. Progress in Energy and Combustion Science, Vol. 37, Issue 5 https://doi.org/10.1016/j.pecs.2010.12.001	journal	September 2011
Molecular Parameters for Normal Fluids. Lennard-Jones 12-6 Potential Tee, L. S.; Gotoh, Sukehiro; Stewart, W. E. Industrial & Engineering Chemistry Fundamentals, Vol. 5, Issue 3 https://doi.org/10.1021/i160019a011	journal	August 1966
Effect of Molecular Configuration on Binary Diffusion Coefficients of Linear Alkanes Chae, Kyungchan; Elvati, Paolo; Violi, Angela The Journal of Physical Chemistry B, Vol. 115, Issue 3 https://doi.org/10.1021/jp109042q	journal	January 2011
Theoretical Unimolecular Kinetics for CH ₄ + M ⇄ CH ₃ + H + M in Eight Baths, M = He, Ne, Ar, Kr, H ₂ , N ₂ , CO, and CH ₄ Jasper, Ahren W.; Miller, James A. The Journal of Physical Chemistry A, Vol. 115, Issue 24 https://doi.org/10.1021/jp200048n	journal	June 2011
Collisional Energy Transfer in Unimolecular Reactions: Direct Classical Trajectories for CH ₄ ⇄ CH ₃ + H in Helium Jasper, Ahren W.; Miller, James A. The Journal of Physical Chemistry A, Vol. 113, Issue 19 https://doi.org/10.1021/jp900802f	journal	May 2009
Army ants algorithm for rare event sampling of delocalized nonadiabatic transitions by trajectory surface hopping and the estimation of sampling errors by the bootstrap method Nangia, Shikha; Jasper, Ahren W.; Miller, Thomas F. The Journal of Chemical Physics, Vol. 120, Issue 8 https://doi.org/10.1063/1.1641019	journal	February 2004
Numerical Evaluation of Quantum Effects on Transport Cross Sections Imam‐Rahajoe, S.; Curtiss, C. F.; Bernstein, R. B. The Journal of Chemical Physics, Vol. 42, Issue 2 https://doi.org/10.1063/1.1695968	journal	January 1965
Automatic Calculation of the Transport Collision Integrals with Tables for the Morse Potential Smith, Francis J.; Munn, R. J. The Journal of Chemical Physics, Vol. 41, Issue 11 https://doi.org/10.1063/1.1725768	journal	December 1964
Relaxation Effects in the Transport Properties of a Gas of Rough Spheres Monchick, L.; Yun, K. S.; Mason, E. A. The Journal of Chemical Physics, Vol. 38, Issue 6 https://doi.org/10.1063/1.1733846	journal	March 1963
The Intermolecular Potentials for Some Simple Nonpolar Molecules Mason, Edward A.; Rice, William E. The Journal of Chemical Physics, Vol. 22, Issue 5 https://doi.org/10.1063/1.1740200	journal	May 1954
Gaseous Diffusion Coefficients Marrero, T. R.; Mason, E. A. Journal of Physical and Chemical Reference Data, Vol. 1, Issue 1 https://doi.org/10.1063/1.3253094	journal	January 1972
Close‐coupling calculations of transport and relaxation cross sections for H2 in Ar Hutson, Jeremy M.; McCourt, Frederick R. The Journal of Chemical Physics, Vol. 80, Issue 3 https://doi.org/10.1063/1.446843	journal	February 1984
H–N ₂ interaction energies, transport cross sections, and collision integrals Stallcop, James R.; Partridge, Harry; Walch, Stephen P. The Journal of Chemical Physics, Vol. 97, Issue 5 https://doi.org/10.1063/1.463956	journal	September 1992
Exact quantum scattering calculation of transport properties for free radicals: OH( X ² Π)–helium Dagdigian, Paul J.; Alexander, Millard H. The Journal of Chemical Physics, Vol. 137, Issue 9 https://doi.org/10.1063/1.4748141	journal	September 2012
Theoretical study of the vibrational relaxation of the methyl radical in collisions with helium Dagdigian, Paul J.; Alexander, Millard H. The Journal of Chemical Physics, Vol. 138, Issue 10 https://doi.org/10.1063/1.4794167	journal	March 2013
Exact quantum scattering calculations of transport properties: CH ₂ (X̃3 B ₁ , ã1 A ₁ )–helium Dagdigian, Paul J.; Alexander, Millard H. The Journal of Chemical Physics, Vol. 138, Issue 16 https://doi.org/10.1063/1.4801789	journal	April 2013
Exact quantum scattering calculations of transport properties for the H ₂ O–H system Dagdigian, Paul J.; Alexander, Millard H. The Journal of Chemical Physics, Vol. 139, Issue 19 https://doi.org/10.1063/1.4829681	journal	November 2013
Erratum: “Global ab initio ground-state potential energy surface of N ₄ ” [J. Chem. Phys. 139, 044309 (2013)] Paukku, Yuliya; Yang, Ke R.; Varga, Zoltan The Journal of Chemical Physics, Vol. 140, Issue 1 https://doi.org/10.1063/1.4861562	journal	January 2014
Communication: A benchmark-quality, full-dimensional ab initio potential energy surface for Ar-HOCO Conte, Riccardo; Houston, Paul L.; Bowman, Joel M. The Journal of Chemical Physics, Vol. 140, Issue 15 https://doi.org/10.1063/1.4871371	journal	April 2014
Permutationally invariant potential energy surfaces in high dimensionality Braams, Bastiaan J.; Bowman, Joel M. International Reviews in Physical Chemistry, Vol. 28, Issue 4 https://doi.org/10.1080/01442350903234923	journal	October 2009
Classical Theory of Transport Phenomena in Dilute Polyatomic Gases Taxman, N. Physical Review, Vol. 110, Issue 6 https://doi.org/10.1103/PhysRev.110.1235	journal	June 1958
Effective potential energies and transport cross sections for interactions of hydrogen and nitrogen Stallcop, James; Partridge, Harry; Levin, Eugene Physical Review A, Vol. 62, Issue 6 https://doi.org/10.1103/PhysRevA.62.062709	journal	November 2000
Statistical-Mechanical Theory of Irreversible Processes. I. General Theory and Simple Applications to Magnetic and Conduction Problems Kubo, Ryogo Journal of the Physical Society of Japan, Vol. 12, Issue 6 https://doi.org/10.1143/JPSJ.12.570	journal	June 1957
Bootstrap Methods: Another Look at the Jackknife Efron, B. The Annals of Statistics, Vol. 7, Issue 1 https://doi.org/10.1214/aos/1176344552	journal	January 1979
Tables of collision integrals for the (m,6) potential function for 10 values of m Klein, Max; Smith, Francis J. Journal of Research of the National Bureau of Standards Section A: Physics and Chemistry, Vol. 72A, Issue 4 https://doi.org/10.6028/jres.072A.033	journal	July 1968

Cited By (1)

Understanding the breakdown of classic two-phase theory and spray atomization at engine-relevant conditions Dahms, Rainer N. Physics of Fluids, Vol. 28, Issue 4 https://doi.org/10.1063/1.4946000	journal	April 2016

Similar Records

First-principles binary diffusion coefficients for H, H{sub 2}, and four normal alkanes + N{sub 2}

Journal Article · Sun Sep 28 00:00:00 EDT 2014 · Journal of Chemical Physics · OSTI ID:22308237

Molecule--molecule collisions: Semiclassical calculations of rotational excitation for the H/sub 2/--CO/sub 2/ system using the exponential approximation

Journal Article · Mon Feb 14 23:00:00 EST 1977 · J. Chem. Phys.; (United States) · OSTI ID:7130498

Investigations of perturbative curved path computational schemes for the calculation of H/sub 2/O--N/sub 2/ collision broadening. [Dipole-quadrupole interaction, resonance]

Thesis/Dissertation · Wed Dec 31 23:00:00 EST 1975 · OSTI ID:7311851

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
anisotropy
combustion
diffusion
intermolecular potentials
potential energy surfaces