How perfluorination alters PAH stability: Benchmarking DFT with CCSD(T) isomerization energies of perfluorinated PAHs

IF 2 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics Pub Date : 2025-03-24 DOI:10.1016/j.chemphys.2025.112712

Amir Karton , Kasimir P. Gregory , Bun Chan

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Abstract

We construct a comprehensive database of CCSD(T) isomerization energies of 64 polycyclic aromatic fluorinated compounds using the G4(MP2) composite ab initio method. This database includes a diverse range of structural motifs, including planar and non-planar configurations, and exhibits unique stability trends influenced by steric effects and F•••F repulsion. Perfluorination significantly alters the relative stabilities of polycyclic aromatic hydrocarbon isomers, with some isomer sets exhibiting near-complete reversals in energetic ordering. We use the G4(MP2) benchmark isomerization energies to evaluate the performance of DFT functionals. D4 dispersion corrections are critical for attaining mean absolute deviations (MADs) below the threshold of chemical accuracy. The best-performing functionals from each rung of Jacob's Ladder are (MADs given in parentheses): BLYP-D4 (4.5), M06-L-D4 (4.8), B3PW91-D4 (3.4), and PW6B95-D4 (3.3 kJ mol⁻¹). This study underscores the current limitations of many DFT functionals and provides critical guidance for future studies on electron-deficient aromatic systems, including perfluorinated nanomaterials.

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来源期刊

Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

4.60

自引率

4.30%

发文量

278

审稿时长

39 days

期刊介绍： Chemical Physics publishes experimental and theoretical papers on all aspects of chemical physics. In this journal, experiments are related to theory, and in turn theoretical papers are related to present or future experiments. Subjects covered include: spectroscopy and molecular structure, interacting systems, relaxation phenomena, biological systems, materials, fundamental problems in molecular reactivity, molecular quantum theory and statistical mechanics. Computational chemistry studies of routine character are not appropriate for this journal.