The Intermolecular Interactions of Pyrene and its Oxides in Vacuum and in Toluene Solution

21 March 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

In this work, the Conformer-Rotamer Ensemble Sampling Tool, (CREST) with the underlying semi-empirical GFN2-xtb method was used for automated geometry exploration of the homodimers of pyrene, pyrene-4,5-dione, and pyrene-4,5,9,10- tetraone, along with the heterodimer of pyrene and pyrene-4,5,9,10-tetraone. Geometries and energies of the dimers were further refined at the ωB97X-D4/def2-TZVP level of theory, both in gas phase, and in toluene solution. Computations in solu- tions were handled using the CPCM (Conductor-like Polarizible Continuum Model) and SMD (Solvation Model based on Density) models. Two previously unidentified pyrene-homodimer conformations are identified, and the effects of oxidation on the geometries and energies of dimerization are explored; in general, oxidation leads to stronger intermolecular interactions, and decreased solubility in toluene. For selected dimers, DLPNO-CCSD(T)/cc-pVTZ/SMD(Toluene) energies are determined at the DFT geometries, and illustrate the accuracy of the ωB97X-D4 approach, with an MAD of 1.47 kJ/mol.

Keywords

Asphaltene
Pyrene
non-covalent interaction
dimerization

Supplementary materials

Title
Description
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Title
Supplementary Information: The Intermolecular Interactions of Pyrene and its Oxides in Vacuum and in Toluene Solution
Description
Gas phase ensembles for (pyrene dione)2, (pyrene tetraone)2, and the pyrene/pyrene-tetraone heterodimer, LED of selected intermolecular interactions, and a CREST to DFT ensemble comparison for the pyrene dimer
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Title
Supplementary Information: xyz coordinates for all conformers
Description
xyz coordinates for all conformers
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