Theoretical study of bromine halocarbons: Accurate enthalpies of formation

Jorgensen, Kameron R.; Cadena, Melissa

doi:10.1016/j.comptc.2018.08.016

“…To evaluate the accuracy of our automated workflow in calculating using the G4 method, 400 enum-halocarb4 species were benchmarked against literature data. Figure shows the distribution of the error for the benchmark set compared to reference from the Active Thermochemical Tables (ATcT) and various literature sources. − ,− ,− , With a mean absolute error (0.83 kcal/mol) within chemical accuracy (≤1 kcal/mol), G4 is a suitable, relatively low-cost composite quantum chemistry method for high-fidelity and high-throughput calculations of HHCs. However, for heavily halogenated systems, G4 and other composite methods do not compute enthalpies within chemical accuracy .…”

Section: Resultsmentioning

confidence: 99%

“…Δ °from the Active Thermochemical Tables (ATcT) 13 and various literature sources. [17][18][19][20][21][22][26][27][28][31][32][33][34]55 With a mean absolute error (0.83 kcal/mol) within chemical accuracy (≤1 kcal/mol), G4 is a suitable, relatively low-cost composite quantum chemistry method for high-fidelity and high-throughput calculations of HHCs. However, for heavily halogenated systems, G4 and other composite methods do not compute enthalpies within chemical accuracy.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Extensive High-Accuracy Thermochemistry and Group Additivity Values for Halocarbon Combustion Modeling

Farina

¹

,

Sirumalla

²

,

Mazeau

³

et al. 2021

Ind. Eng. Chem. Res.

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Standard enthalpies, entropies, and heat capacities are calculated for 16 813 halocarbons using an automated high-fidelity thermochemistry workflow. This workflow generates conformers at density functional tight-binding (DFTB) level, optimizes geometries, calculates harmonic frequencies, and performs 1D hindered rotor scans at DFT level, and computes electronic energies at a Gaussian 4 (G4) level. The computed enthalpies of formation for 400 molecules show good agreement with literature references, but the majority of the calculated species have no reference in the literature. Thus, this work presents G4-computed thermochemistry for thousands of novel halocarbons. This new data set is used to train an extensive ensemble of group additivity values and hydrogen bond increment groups within the Reaction Mechanism Generator (RMG) framework. On average, the new group values estimate standard enthalpies for halogenated hydrocarbons within 3 kcal/mol of their G4 values. A significant contribution toward automated mechanism generation of halocarbon combustion, this research provides thermochemical data for thousands of novel halogenated species and presents a self-consistent set of halogen group additivity values.

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“…from the Active Thermochemical Tables (ATcT) 47 and various literature sources. [13][14][15][16][17][18][22][23][24][27][28][29][30] With a mean absolute error (0.83 kcal/mol) within chemical accuracy (≤ 1 kcal/mol), G4 is a suitable, relatively low cost composite quantum chemistry method for high-fidelity and high-throughput calculations of HHCs. However, for heavily halogenated systems, G4 and other composite methods do not compute enthalpies within chemical accuracy.…”

Section: Kmentioning

confidence: 99%

Extensive High-Accuracy Thermochemistry and Group Additivity Values for Halocarbon Combustion Modeling

Farina

¹

,

Sirumalla

²

,

Mazeau

³

et al. 2021

Preprint

View full text Add to dashboard Cite

Standard enthalpies, entropies, and heat capacities are calculated for 16,813 halocarbons using an automated high-fidelity thermochemistry workflow. This workflow generates conformers at density functional tight binding (DFTB) level, optimizes geometries, calculates harmonic frequencies, and performs 1D hindered rotor scans at DFT level, and computes electronic energies at G4 level. The computed enthalpies of formation for 400 molecules show good agreement with literature references, but the majority of the calculated species have no reference in the literature. Thus, this work presents the most accurate thermochemistry for many halocarbons to date. This new data set is used to train an extensive ensemble of group additivity values and hydrogen bond increment groups within the Reaction Mechanism Generator (RMG) framework. On average, the new group values estimate standard enthalpies for halogenated hydrocarbons within 3 kcal/mol of their G4 values. A significant contribution towards automated mechanism generation of halocarbon combustion, this research provides thermochemical data for thousands of novel halogenated species and presents a self-consistent set of halogen group additivity values.

show abstract

“…from the Active Thermochemical Tables (ATcT) 47 and various literature sources. [13][14][15][16][17][18][22][23][24][27][28][29][30] With a mean absolute error (0.83 kcal/mol) within chemical accuracy (≤ 1 kcal/mol), G4 is a suitable, relatively low cost composite quantum chemistry method for high-fidelity and high-throughput calculations of HHCs. However, for heavily halogenated systems, G4 and other composite methods do not compute enthalpies within chemical accuracy.…”

Section: Kmentioning

confidence: 99%

Extensive High-Accuracy Thermochemistry and Group Additivity Values for Halocarbon Combustion Modeling

Farina

¹

,

Sirumalla

²

,

Mazeau

³

et al. 2021

Preprint

0

View full text Add to dashboard Cite

Standard enthalpies, entropies, and heat capacities are calculated for 16,813 halocarbons using an automated high-fidelity thermochemistry workflow. This workflow generates conformers at density functional tight binding (DFTB) level, optimizes geometries, calculates harmonic frequencies, and performs 1D hindered rotor scans at DFT level, and computes electronic energies at G4 level. The computed enthalpies of formation for 400 molecules show good agreement with literature references, but the majority of the calculated species have no reference in the literature. Thus, this work presents the most accurate thermochemistry for many halocarbons to date. This new data set is used to train an extensive ensemble of group additivity values and hydrogen bond increment groups within the Reaction Mechanism Generator (RMG) framework. On average, the new group values estimate standard enthalpies for halogenated hydrocarbons within 3 kcal/mol of their G4 values. A significant contribution towards automated mechanism generation of halocarbon combustion, this research provides thermochemical data for thousands of novel halogenated species and presents a self-consistent set of halogen group additivity values.

show abstract

Theoretical study of bromine halocarbons: Accurate enthalpies of formation

Cited by 7 publications

References 59 publications

Extensive High-Accuracy Thermochemistry and Group Additivity Values for Halocarbon Combustion Modeling

Extensive High-Accuracy Thermochemistry and Group Additivity Values for Halocarbon Combustion Modeling

Extensive High-Accuracy Thermochemistry and Group Additivity Values for Halocarbon Combustion Modeling

Extensive High-Accuracy Thermochemistry and Group Additivity Values for Halocarbon Combustion Modeling

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