Insight into The Nature of Rim Bonds in Coronene

Abstract

Coronene is known in chemistry as an aromatic or even superaromatic molecule while it has 24 π-electrons which does not conform to the 4n + 2 Huckel’s rule. Chemical bonding description of it is not settled in chemistry and five models were reported in the literature. According to our model, coronene has two concentric π-systems responsible for aromaticity inside of the molecule. In addition to that there are six peripheral 2c–2e π-bonds, which makes coronene aliphatic/aromatic at the same time. However, recent experiments and calculations put in question the presence of peripheral π-bonds. In order to resolve this issue, we computationally studied reaction mechanism of the Cl2 molecule with C2H4, C6H6, and C24H12. As it turned out, coronene behaves in a way similar to ethylene by adding Cl2 molecule. Thus, it proves that coronene indeed has peripheral double bonds which is also consistent with its experimental geometrical features. Our chemical bonding model allows to identify the most reactive atoms in coronene and other PAHs; therefore, it is a matter of importance for combustion and soot formation studies.

Reply to the Comment on “Realization of Lewis Basic Sodium Anion in the NaBH3− Cluster”

“…Correspondence deciphering chemical bonding in non-trivial clusters, [34][35][36][37][38][39][40][41][42][43][44][45][46][47] molecules [48,49] and solids. [50][51][52][53][54] Advantage of the AdNDP method is in its capability to reproduce illustrative Lewis-like structure accepted by broad chemical audience while QTAIM approach is meaningful for those having solid background in theoretical chemistry.T herefore,weemphasize that AdNDP is more appropriate for studying the bonding picture in such compounds.I ta lso worth mentioning that that AdNDP results are also almost independent of method and basis set.…”

Expansion of Magnetic Aromaticity Criteria to Multilayer Structures: Magnetic Response and Spherical Aromaticity of Matryoshka‐Like Cluster [Sn@Cu12@Sn20]12−

“…The induced magnetic field is related to the shielding tensor by the relation B ind [31,36,[60][61][62] in which i and j are related to the x, y,a nd z axes to account for different representative orientations of the external field B ext .B onding analysis was carried out by using the AdNDP code, [63,64] af lexible tool based on the NBO [65][66][67] analysis and capable of recovering both localized and delocalized bonds to get intuitive Lewis-like pictures. [68][69][70][71][72][73] AdNDP analysis was carried out at the MN15L/def2-TZVP [74,75] and CAM-B3LYP/def2-TZVP [76] levels of theory by using Gaussian 16. [77] Our reoptimization at the MN15L/def2-TZVP level of theory did not change the original geometry [22] significantly and showed its vibrational stability,w hich is full in agreement with the results obtained at the TZ2P-PBE/ZORA level of theory.P reviously,t he MN15L functional was used for bonding analysis in [Pd 3 Sn 8 Bi 6 ] 4À and proven to produce ac redible electronic structure alongside with time-tested PBE0 functional.…”

“…The induced magnetic field is related to the shielding tensor by the relation , in which i and j are related to the x , y , and z axes to account for different representative orientations of the external field B ext . Bonding analysis was carried out by using the AdNDP code, a flexible tool based on the NBO analysis and capable of recovering both localized and delocalized bonds to get intuitive Lewis‐like pictures . AdNDP analysis was carried out at the MN15L/def2‐TZVP and CAM‐B3LYP/def2‐TZVP levels of theory by using Gaussian 16 .…”

Reply to the Comment on “Realization of Lewis Basic Sodium Anion in the NaBH3− Cluster”

“…In our original work, we corroborated the Na − :→B assignment, which was based on the minimum‐energy rupture analysis, with both QTAIM and AdNDP analysis. The AdNDP (Adaptive Natural Density Partitioning) method has been very successful in deciphering chemical bonding in non‐trivial clusters, molecules and solids . Advantage of the AdNDP method is in its capability to reproduce illustrative Lewis‐like structure accepted by broad chemical audience while QTAIM approach is meaningful for those having solid background in theoretical chemistry.…”

“…deciphering chemical bonding in non-trivial clusters, [34][35][36][37][38][39][40][41][42][43][44][45][46][47] molecules [48,49] and solids. [50][51][52][53][54] Advantage of the AdNDP method is in its capability to reproduce illustrative Lewis-like structure accepted by broad chemical audience while QTAIM approach is meaningful for those having solid background in theoretical chemistry.T herefore,weemphasize that AdNDP is more appropriate for studying the bonding picture in such compounds.I ta lso worth mentioning that that AdNDP results are also almost independent of method and basis set.…”