Theoretical study of the valence π → π* excited states of polyacenes: Anthracene and naphthacene

Yukio Kawashima, Tomohiro Hashimoto, Haruyuki Nakano, Kimihiko Hirao

Research output: Contribution to journalArticle

74 Citations (Scopus)

Abstract

The valence π → π* excited states of anthracene and naphthacene are studied with multireference perturbation theory with complete active space self-consistent field reference functions. The predicted spectra provide a consistent assignment of all one-and two-photon spectra and T-T spectra of low-lying valence π → π* excited states of anthracene and naphthacene. The present theory predicts the valence π → π* excitation energies with an accuracy of 0.15 eV for anthracene and of 0.25 eV or better for naphthacene. The excited states of anthracene and naphthacene are compared with those of benzene and naphthalene studied previously. The present calculations predict that, going from anthracene to naphthacene, there is a symmetry reversal of the two lowest singlet state transitions, but not for the triplet, just as indicated by the experimental data. Some general trends of polyacene excited states are discussed based on the calculated results for benzene to naphthacene. Conclusive results obtained for anthracene and naphthacene can be used as a model for understanding the excited states of larger polyacenes.

Original languageEnglish
Pages (from-to)49-64
Number of pages16
JournalTheoretical Chemistry Accounts
Volume102
Issue number1-6
DOIs
Publication statusPublished - Jun 1999
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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