S0 and S1 spectroscopy of jet cooled 9-cyano-10-methylanthracene: The methyl group as a molecular rotor

A. Mordziński, A. Leś, Y. Stepanenko, J. Rycombel, L. Adamowicz

Research output: Contribution to journalArticle

4 Scopus citations

Abstract

Jet-cooled fluorescence excitation and dispersed fluorescence spectra of 9-methylanthracene (MA), 9-cyanoanthracene (CA) and 9-cyano-10-methylanthracene (CMA) have been measured. The spectra of MA and CMA near the S 0-S1 origin reveal a prominent torsional progression due to the hindered methyl group rotation and its torsional vibration against the aromatic ring frame. Additionally, the laser induced fluorescence LIF excitation spectrum of CMA shows the splitting of many vibrational modes. Observed positions and relative intensities of the methyl internal rotational bands were interpreted in terms of transitions calculated based on the quantum mechanical one-dimensional rotor. The low-frequency vibrational bands were interpreted also with the all electron quantum mechanical calculations within the RHF/6-31G(d,p), CIS/3-21G and CIS/6-31G(d,p) approximations. It is predicted that in the case of MA the eclipsed geometry (one C-H in the plane of the ring) is most stable in both S0 and S1 states. Conformation of the methyl group in CMA is suggested to change upon S1 ← S 0 excitation (π/12 phase shift of the methyl group). The predicted energy barrier for methyl group rotation in the S0 state of CMA is considerably higher (72 cm-1) than that in the S1 state (22 cm-1). Following the present quantum mechanical calculations, the carbon atom of the methyl group belongs to the aromatic plane in the S 0 ground state but it deviates from this plane in the S1 excited state. These in turn suggest that the calculated barrier for methyl group rotation in CMA has a 6-fold symmetry in the S0 ground state and roughly a 4-fold symmetry in the S1 state.

Original languageEnglish (US)
Pages (from-to)98-109
Number of pages12
JournalJournal of Molecular Spectroscopy
Volume233
Issue number1
DOIs
StatePublished - Sep 1 2005

Keywords

  • Jet spectroscopy
  • Methyl group rotation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Spectroscopy
  • Physical and Theoretical Chemistry

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