Absorption spectra of polycyclic aromatic hydrocarbons have been simulated by using a real-time generating function method that combines adiabatic electronic excitation energies with vibrational energies of the excited states.

Magnetically induced current densities and ring-current pathways have been calculated at density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2) levels of theory for a set of expanded porphyrins consisting of five or six pyrrolic rings. The studied molecules are sapphyrin, cyclo[6]pyrrole, rubyrin, orangarin, rosarin, and amethyrin. Different functionals have been employed to assess the functional dependence of the ring-current strength susceptibility. Vertical singlet and triplet excitation energies have been calculated at the second-order approximate coupled cluster (CC2), expanded multiconfigurational quasi-degenerate perturbation theory (XMC-DPT2), and time-dependent density functional theory levels. The lowest electronic transition of the antiaromatic molecules was found to be pure magnetic transitions providing an explanation for the large paratropic contribution to the total current density. Rate constants for different nonradiative deactivation channels of the lowest excited states have been calculated yielding lifetimes and quantum yields of the lowest excited singlet and triplet states. The calculations show that the spin-orbit interaction between the lowest singlet ( S) and triplet ( T) states of the antiaromatic molecules is strong, whereas for the aromatic molecule the spin-orbit coupling vanishes. The experimentally detected fluorescence from S to S of amethyrin has been explained. The study shows that there are correlations between the aromatic character and optical properties of the investigated expanded porphyrins.

Magnetically induced current densities have been calculated and analyzed for a number of synthesized carbachlorins and carbaporphyrins using density functional theory and the gauge including magnetically induced current (GIMIC) method. Aromatic properties have been determined by using accurate numerical integration of the current flow yielding reliable current strengths and pathways that are related to the degree of aromaticity and the aromatic character of the studied molecules. All investigated compounds are found to be aromatic. However, the obtained aromatic pathways differ from those previously deduced from spectroscopic data and magnetic shielding calculations. For all studied compounds, the ring current divides into an outer and an inner branch at each pyrrolic subring, showing that all π-electrons of the pyrrolic rings take part in the delocalization pathway. The calculations do not support the common notion that the main share of the current takes the inner route at the pyrrolic rings without an inner hydrogen and follows an 18π aromatic pathway. The aromatic pathways of the investigated carbaporphyrins and carbachlorins are very similar, since the current strength via the Cβ[double bond, length as m-dash]Cβ' bond of the cyclopentadienyl ring of the carbaporphyrins is almost as weak as the current density passing the corresponding saturated Cβ-Cβ' bond of the carbachlorins.

The aromaticity of three nonplanar, fully conjugated aza-nanographenes built around a pyrrolo [3,2-b]pyrrole core is assessed through the application of two different computational proceduresGIMIC and NICS. We examine the calculated magnetically induced current densities (GIMIC) and nucleus-independent chemical shifts (NICS). The structural differences between these three apparently similar molecules lead to significantly different aromatic properties. GIMIC analysis indicates that the peripheral diatropic ring current of 3.9 nA/T for the studied bowl-shaped diaza-nanographene is the strongest, followed by the double [6]helicene which lacks seven-membered rings, and is practically nonexistent for the double [5]helicene possessing seven-membered rings. The biggest difference however is that in the two not-fully-fused molecules, the central pyrrole rings possess a significant diatropic current of about 4.1 nA/T, whereas there is no such current in the diaza-nanographene. Moreover, the antiaromaticity of the sevenmembered rings is increasing while moving from double [5]helicene to diaza-nanographene (from −2.4 to −6.0 nA/T). The induced currents derived from NICS π,zz -XY-scan analysis for all of the studied systems are in qualitative agreement with the GIMIC results. Subtle differences may originate from σ-electron currents in GIMIC or inaccuracy of NICS π,zz values due to the nonplanarity of the systems, but the general picture is similar.

Magnetically induced current densities have been calculated for porphycenes at the density functional theory (DFT) level using gauge-including atomic orbitals to ensure gauge-origin independence and a fast basis-set convergence of the current densities. The current densities have been analyzed by using the gauge-including magnetically induced current (GIMIC) method. The porphycenes are aromatic sustaining strong diatropic ring currents. The ring-current pathways have been determined by integrating the strength of the current density passing selected bonds. The calculations show that the ring current of the porphycenes splits into an outer and inner branch at the pyrrolic rings implying that the ring current involves all 26 π electrons of the porphycenes, which is similar to the ring current of porphyrins. The pyrrolic rings of the aromatic porphycenes do not sustain any significant local ring currents. Dihydroporphycene with four inner hydrogens is antiaromatic with weakly aromatic pyrrolic rings. The annelated benzoic rings in benzoporphycene sustain local paratropic ring-currents, whereas the global ring current of dibenzoporphycene splits into an outer and inner branch at the benzoic rings. Comparison of calculated 1 H NMR shieldings with ringcurrent strengths shows that interactions between the inner hydrogen and the neighbor nitrogen is more significant for differences in the 1 H NMR shieldings than variations in global ring-current strengths. Calculated excitation energies show that the antiaromatic dihydroporphycene has a smaller optical gap than the aromatic porphycene, even though its HOMO-LUMO gap is larger. 1 Introduction Vogel et al. performed systematic studies of novel kinds of aromatic porphyrin structures in the mid-1980s, which led to the discovery of porphycene. 1 Porphycenes are a class of compounds that is reminiscent of porphyrin with four linked pyrrolic rings forming a central 16-membered macroring and an outer annulene ring with 20π electrons. Waluk et al. showed later that the electronic structure and the aromatic properties of porphycenes can