Quantum chemical investigation of excited state aromaticity and antiaromaticity effects in organic molecules
Title: Quantum chemical investigation of excited state aromaticity and antiaromaticity effects in organic molecules
SNIC Project: SNIC 2020/5-154
Project Type: SNIC Medium Compute
Principal Investigator: Henrik Ottosson <henrik.ottosson@kemi.uu.se>
Affiliation: Uppsala universitet
Duration: 2020-07-30 – 2021-08-01
Classification: 10405 10407 10402
Homepage: http://www.kemi.uu.se/research/molecular-biomimetic/molecular-inorganic-chemistry/ottosson-group/
Keywords:

Abstract

The project is directed towards aromaticity effects in electronically excited states. We apply quantum chemical calculations using DFT and electron correlated wave function methods (primarily CASSCF and CASPT2, as well as coupled cluster methods). The calculations are closely connected to on-going experimental studies in the group. The topic concerns excited state aromaticity and it is based on Baird's rule which tells that species with 4n pi-electrons are aromatic and those with 4n+2 pi-electrons are antiaromatic in the lowest pipi* excited triplet and singlet states. A series of processes and properties can be examined and rationalized in terms of excited state aromaticity. In the next grant period we will use calculations (i) to examine the impact of singlet excited state (anti)aromaticity on photochemical processes; (ii) investigate the excited states of heteroaromatic compounds in terms of aromaticity and antiaromaticity, (iii) investigate the role of excited state (anti)aromaticity on photochemical reactivity and theoretically assist the development of new photochemical reactions, in particular, drug photodegradation; (iv) to design organic dyes for singlet fission photovoltaics; (v) to screen potential triplet state quenchers for fluorophore bioimaging; (vi) to investigate the importance of aromaticity in porphyrinoids and other macrocycles; (vii) to investigate the importance and interplay of Baird and Clar structures on high-spin polycyclic aromatic hydrocarbons.