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High-Accuracy Heats of Formation for Alkane Oxidation: From Small to Large via the Automated CBH-ANL Method

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [1];  [2];  [2];  [2];  [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. National University of Ireland, Galway (Ireland)
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It is generally challenging to obtain high-accuracy predictions for the heat of formation for species with more than a handful of heavy atoms, such as those of importance in standard combustion mechanisms. To this end, we construct the CBH-ANL approach and illustrate that, for a set of 194 alkane oxidation species, it can be used to produce ΔHf(o K) values with 2σ uncertainties of 0.2-0.5 kcal mol-1. This set includes the alkanes, hydroperoxides, and alkyl, peroxy, and hydroperoxyalkyl radicals for 17 representative hydrocarbon fuels containing up to 10 heavy atoms with various degrees of branching in the alkane backbone. The CBH-ANL approach, automated in the QTC and AutoMech software suites, builds balanced chemical equations for the calculation of ΔHf(o K), in which the reference species may be up to five heavy atoms. The high-level ANLo and ANL1 reference ΔHf(o K) values are further refined for even the largest of these reference species with a novel laddering approach. We perform a comprehensive quantification of the uncertainties for both the individual reference species (the largest of which is 0.15 kcal mol-1) and the propagation of those uncertainties when used in the calculation of ΔHf(o K) for the 194 target species. Here we examine the sensitivity of the predicted ΔHf(o K) values to (i) electronic energies from various methods, including ωB97X-D/cc-pVTZ, B2PLYP-D3/cc-pVTZ, CCSD(T)-F12b/cc-pVDZ-F12//B2PLYP-D3/cc-pVTZ, and CCSD(T)-F12b/cc-pVTZ-F12//B2PLYP-D3/cc-pVTZ; (ii) the zero-point vibrational energies (ZPVEs), where we consider harmonic ZPVEs as well as two scaling-based estimates of the anharmonic ZPVEs, all implemented for both ωB97X-D/cc-pVTZ and B2PLYP-D3/cc-pVTZ calculations; (iii) the particular CBH-ANL scheme employed; and (iv) the procedure for choosing the reference conformer for the analyses. The discussion concludes with a summary of the estimated overall uncertainty in the predictions and a validation of the predictions for the alkane subset.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Exascale Computing Project (ECP); Irish Centre for High-End Computing (ICHEC); Science Foundation Ireland (SFI)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1968018
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 6 Vol. 127; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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