Ab Initio Study of Polycyclic Aromatic Hydrocarbons in Their Ground and Excited States

1998 ◽  
Vol 102 (19) ◽  
pp. 3372-3381 ◽  
Author(s):  
John V. Goodpaster ◽  
James F. Harrison ◽  
Victoria L. McGuffin
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Ab Initio ◽  
Excited States ◽  
Aromatic Hydrocarbons ◽  
Ab Initio Study ◽  
Polycyclic Aromatic

scholarly journals Exploitation of Baird Aromaticity and Clar’s Rule for Tuning the Triplet Energies of Polycyclic Aromatic Hydrocarbons

Chemistry ◽  
2021 ◽  
Vol 3 (2) ◽  
pp. 532-549
Author(s):  
Felix Plasser
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Excited States ◽  
Aromatic Hydrocarbons ◽  
Density Functional ◽  
Materials Science ◽  
Chemical Shifts ◽  
Qualitative Description ◽  
Triplet States ◽  
Excitation Energies ◽  
Polycyclic Aromatic

Polycyclic aromatic hydrocarbons (PAH) are a prominent substance class with a variety of applications in molecular materials science. Their electronic properties crucially depend on the bond topology in ways that are often highly non-intuitive. Here, we study, using density functional theory, the triplet states of four biphenylene-derived PAHs finding dramatically different triplet excitation energies for closely related isomeric structures. These differences are rationalised using a qualitative description of Clar sextets and Baird quartets, quantified in terms of nucleus independent chemical shifts, and represented graphically through a recently developed method for visualising chemical shielding tensors (VIST). The results are further interpreted in terms of a 2D rigid rotor model of aromaticity and through an analysis of the natural transition orbitals involved in the triplet excited states showing good consistency between the different viewpoints. We believe that this work constitutes an important step in consolidating these varying viewpoints of electronically excited states.

scholarly journals Exploitation of Baird Aromaticity and Clar's Rule for Tuning the Triplet Energies of Polycyclic Aromatic Hydrocarbons

2021 ◽  
Author(s):  
Felix Plasser
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Excited States ◽  
Aromatic Hydrocarbons ◽  
Density Functional ◽  
Materials Science ◽  
Chemical Shifts ◽  
Qualitative Description ◽  
Triplet States ◽  
Excitation Energies ◽  
Polycyclic Aromatic

Polycyclic aromatic hydrocarbons (PAH) are a prominent substance class with a variety of applications in molecular materials science. Their electronic properties crucially depend on the bond topology in ways that are often highly non-intuitive. Here, we study, using density functional theory, the triplet states of four PAHs based on the biphenylene motif finding dramatically different triplet excitation energies for closely related isomeric structures. These differences are rationalised using a qualitative description of Clar sextets and Baird quartets, quantified in terms of nucleus independent chemical shifts, and represented graphically through a recently developed method for visualising chemical shielding tensors (VIST). These results are further interpreted in terms of a 2D rigid rotor model of aromaticity and through an analysis of the natural transition orbitals involved in the triplet excited states showing good consistency between the different viewpoints. We believe that this work constitutes an important step in consolidating these varying viewpoints of electronically excited states.

Electronically excited states of PANH anions

2015 ◽  
Vol 17 (22) ◽  
pp. 14761-14772 ◽  
Author(s):  
Mallory L. Theis ◽  
Alessandra Candian ◽  
Alexander G. G. M. Tielens ◽  
Timothy J. Lee ◽  
Ryan C. Fortenberry
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Excited States ◽  
Aromatic Hydrocarbons ◽  
Electronically Excited States ◽  
Electronically Excited ◽  
Polycyclic Aromatic ◽  
Derivatives Of

The singly deprotonated anion derivatives of nitrogenated polycyclic aromatic hydrocarbons are shown likely to possess dipole-bound and even valence excited states for the larger systems.

scholarly journals Exploitation of Baird Aromaticity and Clar's Rule for Tuning the Triplet Energies of Polycyclic Aromatic Hydrocarbons

2021 ◽  
Author(s):  
Felix Plasser
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Excited States ◽  
Aromatic Hydrocarbons ◽  
Density Functional ◽  
Materials Science ◽  
Chemical Shifts ◽  
Qualitative Description ◽  
Triplet States ◽  
Excitation Energies ◽  
Polycyclic Aromatic

Polycyclic aromatic hydrocarbons (PAH) are a prominent substance class with a variety of applications in molecular materials science. Their electronic properties crucially depend on the bond topology in ways that are often highly non-intuitive. Here, we study, using density functional theory, the triplet states of four PAHs based on the biphenylene motif finding dramatically different triplet excitation energies for closely related isomeric structures. These differences are rationalised using a qualitative description of Clar sextets and Baird quartets, quantified in terms of nucleus independent chemical shifts, and represented graphically through a recently developed method for visualising chemical shielding tensors (VIST). These results are further interpreted in terms of a 2D rigid rotor model of aromaticity and through an analysis of the natural transition orbitals involved in the triplet excited states showing good consistency between the different viewpoints. We believe that this work constitutes an important step in consolidating these varying viewpoints of electronically excited states.

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