Can Aromaticity Be Evaluated Using Atomic Partitions Based on the Hilbert-Space?

Autor: Grèbol-Tomàs J; Departament de Química, Universitat de Girona, Campus de Montilivi, 17071, Girona, Spain.; Donostia International Physics Center (DIPC), Manuel de Lardizábal 4, 20018, Donostia, Euskadi, Spain., Matito E; Donostia International Physics Center (DIPC), Manuel de Lardizábal 4, 20018, Donostia, Euskadi, Spain.; Ikerbasque Foundation for Science, Bilbao, Euskadi, Spain., Salvador P; Departament de Química, Universitat de Girona, Campus de Montilivi, 17071, Girona, Spain.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Aug 06; Vol. 30 (44), pp. e202401282. Date of Electronic Publication: 2024 Jul 22.
DOI: 10.1002/chem.202401282
Abstrakt: Aromaticity is a fundamental concept in chemistry that explains the stability and reactivity of many compounds by identifying atoms within a molecule that form an aromatic ring. Reliable aromaticity indices focus on electron delocalization and depend on atomic partitions, which give rise to the concept of an atom-in-the-molecule (AIM). Real-space atomic partitions present two important drawbacks: a high computational cost and numerical errors, limiting some aromaticity measures to medium-sized molecules with rings up to 12 atoms. This restriction hinders the study of large conjugated systems like porphyrins and nanorings. On the other hand, traditional Hilbert-space schemes are free of the latter limitations but can be unreliable for the large basis sets required in modern computational chemistry. This paper explores AIMs based on three robust Hilbert-space partitions - meta-Löwdin, Natural Atomic Orbitals (NAO), and Intrinsic Atomic Orbitals (IAO) - which combine the advantages of real-space partitions without their disadvantages. These partitions can effectively replace real-space AIMs for evaluating the aromatic character. For the first time, we report multicenter index (MCI) and I ring values for large rings and introduce ESIpy, an open-source Python code for aromaticity analysis in large conjugated rings.
(© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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