TY - JOUR

T1 - Benchmark Thermochemistry of the CnH2n+2 Alkane Isomers (n = 2—8) and Performance of DFT and Composite Ab Initio Methods for Dispersion-Driven Isomeric Equilibria

AU - Karton, Amir

AU - Gruzman, D.

AU - Martin, J.M.L.

PY - 2009/7/23

Y1 - 2009/7/23

N2 - The thermochemistry of linear and branched alkanes with up to eight carbons has been reexamined by means of W4, W3.2lite and W1h theories. “Quasi-W4” atomization energies have been obtained via isodesmic and hypohomodesmotic reactions. Our best atomization energies at 0 K (in kcal/mol) are 1220.04 for n-butane, 1497.01 for n-pentane, 1774.15 for n-hexane, 2051.17 for n-heptane, 2328.30 for n-octane, 1221.73 for isobutane, 1498.27 for isopentane, 1501.01 for neopentane, 1775.22 for isohexane, 1774.61 for 3-methylpentane, 1775.67 for diisopropyl, 1777.27 for neohexane, 2052.43 for isoheptane, 2054.41 for neoheptane, 2330.67 for isooctane, and 2330.81 for hexamethylethane. Our best estimates for ΔHf,298K° are −30.00 for n-butane, −34.84 for n-pentane, −39.84 for n-hexane, −44.74 for n-heptane, −49.71 for n-octane, −32.01 for isobutane, −36.49 for isopentane, −39.69 for neopentane, −41.42 for isohexane, −40.72 for 3-methylpentane, −42.08 for diisopropyl, −43.77 for neohexane, −46.43 for isoheptane, −48.84 for neoheptane, −53.29 for isooctane, and −53.68 for hexamethylethane. These are in excellent agreement (typically better than 1 kJ/mol) with the experimental heats of formation at 298 K obtained from the CCCBDB and/or NIST Chemistry WebBook databases. However, at 0 K, a large discrepancy between theory and experiment (1.1 kcal/mol) is observed for only neopentane. This deviation is mainly due to the erroneous heat content function for neopentane used in calculating the 0 K CCCBDB value. The thermochemistry of these systems, especially that of the larger alkanes, is an extremely difficult test for density functional methods. A posteriori corrections for dispersion are essential. Particularly for the atomization energies, the B2GP-PLYP and B2K-PLYP double hybrids and the PW6B95 hybrid meta-GGA clearly outperform other DFT functionals.

AB - The thermochemistry of linear and branched alkanes with up to eight carbons has been reexamined by means of W4, W3.2lite and W1h theories. “Quasi-W4” atomization energies have been obtained via isodesmic and hypohomodesmotic reactions. Our best atomization energies at 0 K (in kcal/mol) are 1220.04 for n-butane, 1497.01 for n-pentane, 1774.15 for n-hexane, 2051.17 for n-heptane, 2328.30 for n-octane, 1221.73 for isobutane, 1498.27 for isopentane, 1501.01 for neopentane, 1775.22 for isohexane, 1774.61 for 3-methylpentane, 1775.67 for diisopropyl, 1777.27 for neohexane, 2052.43 for isoheptane, 2054.41 for neoheptane, 2330.67 for isooctane, and 2330.81 for hexamethylethane. Our best estimates for ΔHf,298K° are −30.00 for n-butane, −34.84 for n-pentane, −39.84 for n-hexane, −44.74 for n-heptane, −49.71 for n-octane, −32.01 for isobutane, −36.49 for isopentane, −39.69 for neopentane, −41.42 for isohexane, −40.72 for 3-methylpentane, −42.08 for diisopropyl, −43.77 for neohexane, −46.43 for isoheptane, −48.84 for neoheptane, −53.29 for isooctane, and −53.68 for hexamethylethane. These are in excellent agreement (typically better than 1 kJ/mol) with the experimental heats of formation at 298 K obtained from the CCCBDB and/or NIST Chemistry WebBook databases. However, at 0 K, a large discrepancy between theory and experiment (1.1 kcal/mol) is observed for only neopentane. This deviation is mainly due to the erroneous heat content function for neopentane used in calculating the 0 K CCCBDB value. The thermochemistry of these systems, especially that of the larger alkanes, is an extremely difficult test for density functional methods. A posteriori corrections for dispersion are essential. Particularly for the atomization energies, the B2GP-PLYP and B2K-PLYP double hybrids and the PW6B95 hybrid meta-GGA clearly outperform other DFT functionals.

U2 - 10.1021/jp904369h

DO - 10.1021/jp904369h

M3 - Article

C2 - 19569667

VL - 113

SP - 8434

EP - 8447

JO - The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

SN - 1089-5639

IS - 29

ER -