Group additivity values for the heat of formation of C2–C8 alkanes, alkyl hydroperoxides, and their radicals

Ghosh, Manik Kumer; Elliott, Sarah N.; Somers, Kieran P.; Klippenstein, Stephen J.; Curran, Henry J.

doi:10.1016/j.combustflame.2022.112492

Cited by 12 publications

(3 citation statements)

References 89 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This decomposition can also be conducted in a way to conserve the bonding environment and hybridization, which will lead to an expression similar to that of the isodesmic or homodesmotic reactions from the CBH. In fact, it would be possible to construct group additivity parameters based on the accurate enthalpies of formation derived via the isodesmic bond separation reactions presented in this work, as done by Ghosh and co-workers 76 for gas-phase molecules.…”

Section: ■ Discussionmentioning

confidence: 99%

Linking Experimental and Ab Initio Thermochemistry of Adsorbates with a Generalized Thermochemical Hierarchy

Kreitz

Abeywardane

Goldsmith

2023

J. Chem. Theory Comput.

View full text Add to dashboard Cite

Enthalpies of formation of adsorbates are crucial parameters in the microkinetic modeling of heterogeneously catalyzed reactions since they quantify the stability of intermediates on the catalyst surface. This quantity is often computed using density functional theory (DFT), as more accurate methods are computationally still too expensive, which means that the derived enthalpies have a large uncertainty. In this study, we propose a new error cancellation method to compute the enthalpies of formation of adsorbates from DFT more accurately through a generalized connectivity-based hierarchy. The enthalpy of formation is determined through a hypothetical reaction that preserves atomistic and bonding environments. The method is applied to a data set of 60 adsorbates on Pt(111) with up to 4 heavy (non-hydrogen) atoms. Enthalpies of formation of the fragments required for the bond balancing reactions are based on experimental heats of adsorption for Pt(111). The comparison of enthalpies of formation derived from different DFT functionals using the isodesmic reactions shows that the effect of the functional is significantly reduced due to the error cancellation. Thus, the proposed methodology creates an interconnected thermochemical network of adsorbates that combines experimental with ab initio thermochemistry in a single and more accurate thermophysical database.

show abstract

Section: ■ Discussionmentioning

confidence: 99%

Linking Experimental and Ab Initio Thermochemistry of Adsorbates with a Generalized Thermochemical Hierarchy

Kreitz

Abeywardane

Goldsmith

2023

J. Chem. Theory Comput.

View full text Add to dashboard Cite

show abstract

“…The CBH method alternates between atom-centered and bond-centered conservation, and each new level expands the size of the molecular fragments, thereby ensuring increasing structural similarity to the target species. One particular advantage of the CBH method is that it can be automated. , The CBH method has been adopted by many groups in the combustion community for hydrocarbon enthalpies of formation, − and was recently extended to include adsorbates on metals as well …”

Section: Introductionmentioning

confidence: 99%

Accurate Enthalpies of Formation for PFAS from First-Principles: Combining Different Levels of Theory in a Generalized Thermochemical Hierarchy

Abeywardane,

Goldsmith

2024

ACS Phys. Chem Au

View full text Add to dashboard Cite

The enthalpies of formation are computed for a large number of per-and poly fluoroalkyl substances (PFAS) using a connectivity-based hierarchy (CBH) approach. A combination of different electronic structure methods are used to provide the reference data in a hierarchical manner. The ANL0 method, in conjunction with the active thermochemical tables, provides enthalpies of formation for smaller species with subchemical accuracy. Coupled-cluster theory with explicit correlations are used to compute enthalpies of formation for intermediate species, based upon the ANL0 results. For the largest PFAS, including perfluorooctanoic acid (PFOA) and heptafluoropropylene oxide dimer acid (GenX), coupled-cluster theory with local correlations is used. The sequence of homodesmotic reactions proposed by the CBH are determined automatically by a new open-source code, AUTOCBH. The results are the first reported enthalpies of formation for the majority of the species. A convergence analysis and global uncertainty quantification confirm that the enthalpies of formation at 0 K should be accurate to within ±5 kJ/mol. This new approach is not limited to PFAS, but can be applied to many chemical systems.

show abstract

“…These GAVs then serve to estimate the thermodynamic properties of larger and more complex molecules. The principle of Benson's group additivity theory is demonstrated in Figure 2 Several group additivity schemes to estimate thermodynamic properties have been developed for oxygenated hydrocarbons, such as work by Paraskevas et al, 25 Ghosh et al, 26,27 and Burke et al 28 Paraskevas et al regressed GAVs for 60 nonradical and 97 radical groups based on a data set with properties for 202 nonradical and 248 radical species at the CBS-QB3 level of theory. Furthermore, 26 corrections for non-next-nearest neighbor interactions (NNIs) were introduced.…”

Section: Introductionmentioning

confidence: 99%

Estimating Thermodynamic Properties of Oxymethylene-Ether-like Species Using Group Additivity

De Ras,

Thybaut,

Van Geem

2024

Energy Fuels

View full text Add to dashboard Cite

Group additivity values for the heat of formation of C2–C8 alkanes, alkyl hydroperoxides, and their radicals

Cited by 12 publications

References 89 publications

Linking Experimental and Ab Initio Thermochemistry of Adsorbates with a Generalized Thermochemical Hierarchy

Linking Experimental and Ab Initio Thermochemistry of Adsorbates with a Generalized Thermochemical Hierarchy

Accurate Enthalpies of Formation for PFAS from First-Principles: Combining Different Levels of Theory in a Generalized Thermochemical Hierarchy

Estimating Thermodynamic Properties of Oxymethylene-Ether-like Species Using Group Additivity

Contact Info

Product

Resources

About