The vibronic (vibrational-electronic) interactions and Jahn-Teller distortions in the mono- and trianions and the mono- and trications of coronene are discussed. E2g modes of vibration remove the orbital degeneracies in the highly symmetric D6h molecule to lead to D2h distortions. We calculate and analyze the vibrational modes and the linear vibronic coupling constants of the anions and cations of coronene as well as its deutero-form using the (Becke and Lee, Yang, and Parr) density-functional method. Although there are twelve E2g modes of vibration in coronene, some of them appear to play a significant role in the Jahn-Teller distortions. The lowest frequency mode of 370cm-1, the C-C stretching mode of 1668cm-1, and the C-H stretching modes of 3177 and 3193cm-1 give large coupling constants in the anions. In particular, the 1668cm-1 mode plays the most important role in the Jahn-Teller distortions both in the anions and cations. There is electron-hole symmetry in the coupling constants in the anions and cations. We also demonstrate an important H/D isotope effect. The highest two C-H stretching modes are important for the Jahn-Teller distortions in coronene; however, the corresponding C-D stretching modes are less important for the Jahn-Teller distortions in deutero-coronene.
All Science Journal Classification (ASJC) codes
- General Physics and Astronomy
- Physical and Theoretical Chemistry