A theoretical investigation of valence and Rydberg electronic states of acrolein

Francesco Aquilante, V Barone, Björn Roos

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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.
Original languageEnglish
Pages (from-to)12323-12334
JournalJournal of Chemical Physics
Volume119
Issue number23
DOIs
Publication statusPublished - 2003

Bibliographical note

The information about affiliations in this record was updated in December 2015.
The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)

Subject classification (UKÄ)

  • Theoretical Chemistry

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