Accurate thermochemistry prediction of extensive Polycyclic aromatic hydrocarbons (PAHs) and relevant radicals

Yang Li*, Tairan Wang, Kiran K. Yalamanchi, Goutham Kukkadapu, S. Mani Sarathy

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are important intermediates to soot formation in combustion. A reliable database of their thermochemistry is required for the development of chemical kinetic models describing the gas-phase chemistry of hydrocarbon fuels. In this study, temperature-dependent thermodynamic properties are consistently determined using high-accuracy quantum chemistry calculations for an extensive set of PAH compounds. The developed database comprehensively consists of 125 C6-C18 PAH molecules and radicals, which are important and commonly included in chemical mechanisms studies. At the M06-2X/6-311++G(d,p) level of theory, geometry optimizations, vibrational frequency calculations, and dihedral angle scans are performed for all PAH species. The G3 method, together with the atomization reaction approach, is selected to derive the average atomization formation enthalpy. This method produces the most accurate thermochemistry quantities for PAHs, as demonstrated in a previous study. The entropy and heat capacity values are calculated using statistical thermodynamics in MultiWell. These results exhibit good agreement with the databases in literature. To examine the application of the group additivity (GA) method for PAHs, the Bland−Altman plot, a statistical analysis approach, is employed to visualize the agreement between the results from the quantum chemical calculations and GA methods. Two GA methods are examined and significant differences are found, which indicates that GA values of relevant groups need to be further updated. The database of thermodynamic quantities developed in this study are of particular value in modeling studies and important for exploring mechanisms of the PAH growth.

Original languageEnglish (US)
Article number112159
JournalCombustion and Flame
Volume242
DOIs
StatePublished - Aug 2022

Keywords

  • Enthalpy
  • Entropy
  • Heat capacity
  • PAHs
  • Quantum chemical calculation
  • Thermochemistry

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Fuel Technology
  • Energy Engineering and Power Technology
  • General Physics and Astronomy

Fingerprint

Dive into the research topics of 'Accurate thermochemistry prediction of extensive Polycyclic aromatic hydrocarbons (PAHs) and relevant radicals'. Together they form a unique fingerprint.

Cite this