1. Relevance of the DFT method to study expanded porphyrins with different topologies
- Author
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Josep M. Anglada, Miquel Torrent-Sucarrat, Josep M. Luis, Fernando P. Cossío, Sara Navarro, Ministerio de Economía y Competitividad (Espanya), Ministerio de Economía y Competitividad (España), Universidad del País Vasco, Eusko Jaurlaritza, Generalitat de Catalunya, Torrent‐Sucarrat, Miquel, Cossío, Fernando P., Anglada, Josep M., Luis, Josep M., Torrent‐Sucarrat, Miquel [0000-0003-2689-0278], Cossío, Fernando P. [0000-0002-4526-2122], Anglada, Josep M. [0000-0003-4526-3624], and Luis, Josep M. [0000-0002-2880-8680]
- Subjects
Work (thermodynamics) ,Möbius ,Spurious stationary points ,DLPNO‐CCSD(T) ,010402 general chemistry ,Network topology ,01 natural sciences ,Hückel ,Aromaticity (Chemistry) ,Computational chemistry ,Aromaticitat (Química) ,Point (geometry) ,Statistical physics ,Spurious relationship ,Density functionals ,Funcional de densitat, Teoria del ,010405 organic chemistry ,Chemistry ,Aromaticity ,General Chemistry ,Expanded porphyrin ,Stationary point ,0104 chemical sciences ,Computational Mathematics ,Coupled cluster ,Density functional theory methods ,Potential energy surface ,Density functional theory - Abstract
Meso‐aryl expanded porphyrins present a structural versatility that allows them to achieve different topologies with distinct aromaticities. Several studies appeared in the literature studying these topological switches from an experimental and theoretical point of view. Most of these publications include density functional theory calculations, being the B3LYP the most used methodology. In this work, we show that the selection of the functional has a critical role on the geometric, energetic, and magnetic results of these expanded porphyrins, and that the use of an inadequate methodology can even generate spurious stationary points on the potential energy surface. To illustrate these aspects, in this article we have studied different molecular distortions of two expanded porphyrins, [32]‐heptaphyrin and [26]‐hexaphyrin using 11 DFT functionals and performing single point energy calculations at the local pair natural orbital coupled cluster DLPNO‐CCSD(T) method, which have been carried out for benchmarking purposes. For some selected functionals, the dispersion effects have also been evaluated using the D3‐Grimme's dispersion correction with Becke–Johnson damping. Our results let us to conclude that the CAM‐B3LYP, M05‐2X, and M06‐2X functionals are the methodologies that provide a more consistent description of these topological switches, while other methods, such as B3LYP, BPE, and BP86, show a biased description., Ministerio de Economía y Competitividad of Spain . Grant Numbers: CTQ2016‐80375‐P , CTQ2014‐52525‐P , CTQ2014‐51912‐REDC -Universidad del País Vasco ‐ Euskal Herriko Unibertsitatea (UPV/EHU) . Grant Number: UFI11/22 QOSYC -Basque Government . Grant Number: IT673‐13 -Generalitat de Catalunya . Grant Number: 2014SGR139
- Published
- 2017