Thermochemical stabilities of giant fullerenes using density functional tight binding theory and isodesmic-type reactions

Waite, Simone L.; Karton, Amir; Chan, Bun; Page, Alister J.

Title: Thermochemical stabilities of giant fullerenes using density functional tight binding theory and isodesmic-type reactions
Creator: Waite, Simone L.; Karton, Amir; Chan, Bun; Page, Alister J.
Relation: ARC.FL170100032 http://purl.org/au-research/grants/arc/FL170100032
Relation: Journal of Computational Chemistry Vol. 42, Issue 4, p. 222-230
Publisher Link: http://dx.doi.org/10.1002/jcc.26449
Publisher: John Wiley & Sons
Resource Type: journal article
Date: 2021
Description: We present a systematic assessment of the density functional tight binding (DFTB) method for calculating heats of formation of fullerenes with isodesmic-type reaction schemes. We show that DFTB3-D/3ob can accurately predict Δ_fH values of the 1812 structural isomers of C₆₀, reproduce subtle trends in ΔfH values for 24 isolated pentagon rule (IPR) isomers of C84, and predict Δ_fH values of giant fullerenes that are in effectively exact agreement with benchmark DSD-PBEP86/def2-QZVPP calculations. For fullerenes up to C₃₂₀, DFTB Δ_fH values are within 1.0 kJ mol⁻¹ of DSD-PBEP86/def2-QZVPP values per carbon atom, and on a per carbon atom basis DFTB3-D/3ob yields exactly the same numerical trend of (Δ_fH [per carbon] = 722n^−0.72 + 5.2 kJ mol⁻¹). DFTB3-D/3ob is therefore an accurate replacement for high-level DHDFT and composite thermochemical methods in predicting of thermochemical stabilities of giant fullerenes and analogous nanocarbon architectures.
Subject: density functional tight binding; fullerene; isodesmic reaction; thermochemistry
Identifier: http://hdl.handle.net/1959.13/1460913
Identifier: uon:46067
Identifier: ISSN:0192-8651
Language: eng
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