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Singlet–triplet excitation energies of substituted phenyl cations: a G4(MP2) and G4 theoretical study

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Abstract

Singlet–triplet adiabatic excitation energies (AES−T) of the parent and variously substituted phenyl cations, as well as the parent benzannelated derivatives up to anthracenyl, were calculated at the G4(MP2) and G4 levels of theory. The G4(MP2)/G4 AES−T estimates range up to 40 kJ/mol higher than prior density functional theory (DFT)-based predictions for these cations and suggest that AES−T and ground state multiplicity structure–property trends for phenyl cations previously proposed in the literature need to be re-assessed at higher levels of theory. In general, Hartree–Fock, DFT, and semiempirical methods do a poor job describing the singlet–triplet excitation energetics of these systems. Only modest effects of different solvation models (SMD, IEF-PCM, and C-PCM) and different polar protic through apolar aprotic solvents are evident on the calculated AES−T of the phenyl cation. Electron-donating substituents on the phenyl cation substantially lower the AES−T to an extent where some functional groups (–NH2, N(CH3)2, OCH3, and SCH3) can result in triplet ground states depending on their position relative to the cation. In contrast to the phenyl and 1- and 2-naphthyl cations, which are predicted to be ground state singlets, the three parent anthracenyl cations will be ground state triplets.

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Acknowledgments

This work was made possible by the facilities of the Western Canada Research Grid (WestGrid: project 100185), the Shared Hierarchical Academic Research Computing Network (SHARCNET: project sn4612), and Compute/Calcul Canada.

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Authors and Affiliations

  1. Chemologica Research, 1617-11th Avenue NW, Moose Jaw, SK, S6H 6M5, Canada

    Sierra Rayne

  2. Department of Environmental Engineering Technology, Saskatchewan Polytechnic, 600 Saskatchewan Street West, Moose Jaw, SK, S6H 4R4, Canada

    Kaya Forest

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  1. Sierra Rayne
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  2. Kaya Forest
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Correspondence to Sierra Rayne.

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Rayne, S., Forest, K. Singlet–triplet excitation energies of substituted phenyl cations: a G4(MP2) and G4 theoretical study. Theor Chem Acc 135, 69 (2016). https://doi.org/10.1007/s00214-016-1837-5

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