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  • Corchado, José C. (författare)

Theoretical Study of Solvent Effects on the Ground and Low-Lying Excited Free Energy Surfaces of a Push–Pull Substituted Azobenzene

  • Artikel/kapitelEngelska2014

Förlag, utgivningsår, omfång ...

  • 2014-10-20
  • American Chemical Society (ACS),2014
  • printrdacarrier

Nummerbeteckningar

  • LIBRIS-ID:oai:DiVA.org:uu-238899
  • https://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-238899URI
  • https://doi.org/10.1021/jp506876vDOI

Kompletterande språkuppgifter

  • Språk:engelska
  • Sammanfattning på:engelska

Ingår i deldatabas

Klassifikation

  • Ämneskategori:ref swepub-contenttype
  • Ämneskategori:art swepub-publicationtype

Anmärkningar

  • The ground and low-lying excited free energy surfaces of 4-amino-4'-cyano azobenzene, a molecule that has been proposed as building block for chiroptical switches, are studied in gas phase and a variety of solvents (benzene, chloroform, acetone, and water). Solvent effects on the absorption and emission spectra and on the cistrans thermal and photo isomerizations are analyzed using two levels of calculation: TD-DFT and CASPT2/CASSCF. The solvent effects are introduced using a polarizable continuum model and a QM/MM method, which permits one to highlight the role played by specific interactions. We found that, in gas phase and in agreement with the results found for other azobenzenes, the thermal cistrans isomerization follows a rotation-assisted inversion mechanism where the inversion angle must reach values close to 180 degrees but where the rotation angle can take almost any value. On the contrary, in polar solvents the mechanism is controlled by the rotation of the CN=NC angle. The change in the mechanism is mainly related to a better solvation of the nitrogen atoms of the azo group in the rotational transition state. The photoisomerization follows a rotational pathway both in gas phase and in polar and nonpolar solvents. The solvent introduces only small modifications in the n pi* free energy surface (S-1), but it has a larger effect on the pi pi* surface (S-2) that, in polar solvents, gets closer to S-1. In fact, the S-2 band of the absorption spectrum is red-shifted 0.27 eV for the trans isomer and 0.17 eV for the cis. In the emission spectrum the trend is similar: only S-2 is appreciably affected by the solvent, but in this case a blue shift is found.

Ämnesord och genrebeteckningar

Biuppslag (personer, institutioner, konferenser, titlar ...)

  • Sánchez, M. Luz (författare)
  • Fernández Galván, Ignacio,1977-Uppsala universitet,Teoretisk kemi(Swepub:uu)ignga749 (författare)
  • Martín, M. Elena (författare)
  • Muñoz-Losa, Aurora (författare)
  • Barata-Morgado, Rute (författare)
  • Aguilar, Manuel A. (författare)
  • Uppsala universitetTeoretisk kemi (creator_code:org_t)

Sammanhörande titlar

  • Ingår i:Journal of Physical Chemistry B: American Chemical Society (ACS)118:43, s. 12518-125301520-61061520-5207

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