Theoretical prediction of the vibrational spectrum of naphthalene in the first excited singlet state

Petra Swiderek, Georg Hohlneicher, Sergio A. Maluendes, Michel Dupuis

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

Complete harmonic force fields have been calculated for the ground state (S0) and the first excited singlet state (S1) of naphthalene using the multiconfiguration self-consistent field (MCSCF) approach. Identical calculations were performed for benzene to test the methodology with already available theoretical and empirical force fields. Two different basis sets were applied (STO-3G and near double-zeta) and all π-orbitals included in the active space. The geometries of ground and excited states were separately optimized. Following the ideas of Pulay, the force constants were scaled before calculating frequencies and normal modes. For the ground states the influence of correlation is discussed by comparison with Pulay's results. Except for special vibrations where correlation effects turn out to be important, the use of Pulay's scaling factors leads to a satisfactory description of the in-plane-vibrations. In the case of benzene the calculated frequency shifts between S0 and S1 are in complete qualitative agreement with experimental observations. In the case of naphthalene the new theoretical results suggest several revisions of earlier empirical assignments.

Original languageEnglish
Pages (from-to)974-987
Number of pages14
JournalThe Journal of Chemical Physics
Volume98
Issue number2
DOIs
Publication statusPublished - Jan 1 1993

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'Theoretical prediction of the vibrational spectrum of naphthalene in the first excited singlet state'. Together they form a unique fingerprint.

  • Cite this