A theoretical study of the lowest electronic states of azobenzene: The role of torsion coordinate in the cis-trans photoisomerization

Laura Gagliardi, Giorgio Orlandi, Fernando Bernardi, Alessandro Cembran, Marco Garavelli

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Abstract

In the present paper we report the results of a multiconfigurational computational study on potential-energy curves of azobenzene along the NN twisting to clarify the role of this coordinate in the decay of the S 2(ππ*) and S1(nπ*) states. We have found that there is a singlet state, S3 at the trans geometry, on the basis of the doubly excited configuration n2π*2, that has a deep minimum at about 90° of twisting, where it is the lowest excited singlet state. The existence of this state provides an explanation for the short lifetime of S2(ππ*) and for the wavelength-dependence of azobenzene photochemistry. We have characterized the S1(nπ*) state by calculating its vibrational frequencies, which are found to correspond to the recently observed transient Raman spectrum. We have also computed the potential-energy curve for the triplet T 1(nπ*) at the density functional theory B3LYP level, which indicates that in this state the isomerization occurs along the twisting coordinate.

Original languageEnglish (US)
Pages (from-to)363-372
Number of pages10
JournalTheoretical Chemistry Accounts
Volume111
Issue number2-6
DOIs
StatePublished - Mar 2004

Keywords

  • Azobenzene
  • Excited electronic states
  • Multiconfigurational wave function methods
  • Photoisomerization

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