A theoretical investigation of valence and Rydberg electronic states of acrolein

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Abstract

The main features of the ultraviolet spectrum of acrolein have been studied by a multireference perturbative treatment and by a time dependent density functional approach. The valence and Rydberg transition energies have been calculated and the assignment of the experimental bands has been clarified. The different relaxation trends of the three lowest singlet and triplet excited states have been analyzed by unconstrained geometry optimizations. This has allowed, in particular, the characterization of a twisted 3(*) state, which is crucial for the interesting photophysics and photochemistry of the acrolein molecule and, more generally, of the ,-enones. Solvatochromic shifts in aqueous solution have been investigated using a combined discrete/continuum approach based on the so called polarizable continuum model. The experimental trends are well reproduced by this approach and a closer degeneracy in the triplet manifold has been detected in solution with respect to gas phase. ©2003 American Institute of Physics.

Detaljer

Författare
  • Francesco Aquilante
  • V Barone
  • Björn Roos
Enheter & grupper
Forskningsområden

Ämnesklassifikation (UKÄ) – OBLIGATORISK

  • Teoretisk kemi
Originalspråkengelska
Sidor (från-till)12323-12334
TidskriftJournal of Chemical Physics
Volym119
Utgivningsnummer23
StatusPublished - 2003
PublikationskategoriForskning
Peer review utfördJa