Computational Studies of Aromatic and Photophysical Properties of Expanded Porphyrins

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Valiev , R R , Benkyi , I , Konyshev , Y , Fliegl , H & Sundholm , D 2018 , ' Computational Studies of Aromatic and Photophysical Properties of Expanded Porphyrins ' , Journal of Physical Chemistry A , vol. 122 , no. 20 , pp. 4756-4767 . https://doi.org/10.1021/acs.jpca.8b02311

Title: Computational Studies of Aromatic and Photophysical Properties of Expanded Porphyrins
Author: Valiev, Rashid R.; Benkyi, Isaac; Konyshev, Yuri; Fliegl, Heike; Sundholm, Dage
Contributor: University of Helsinki, Department of Chemistry
University of Helsinki, Department of Chemistry
University of Helsinki, University of Oslo
University of Helsinki, Department of Chemistry
Date: 2018-05-24
Language: eng
Number of pages: 23
Belongs to series: Journal of Physical Chemistry A
ISSN: 1089-5639
URI: http://hdl.handle.net/10138/309481
Abstract: Magnetically induced current densities and ring-current pathways have been calculated at density functional theory (DFT) and second-order Moller-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-0) and triplet (T-1) states of the antiaromatic molecules is strong, whereas for the aromatic molecule the spin-orbit coupling vanishes. The experimentally detected fluorescence from S-2 to S-0 of amethyrin has been explained. The study shows that there are correlations between the aromatic character and optical properties of the investigated expanded porphyrins.
Subject: ZETA VALENCE QUALITY
NMR CHEMICAL-SHIFTS
GAUSSIAN-BASIS SETS
RING CURRENTS
PERTURBATION-THEORY
EXCITED-STATES
ANTIAROMATIC PORPHYRINOIDS
ELECTRON DELOCALIZATION
IDENTITY APPROXIMATION
WORKSTATION COMPUTERS
116 Chemical sciences
113 Computer and information sciences
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