Relative Stability of the L-a and L-b Excited States in Adenine and Guanine: Direct Evidence from TD-DFT Calculations of MCD Spectra
2014 (English)In: Journal of Physical Chemistry Letters, ISSN 1948-7185, E-ISSN 1948-7185, Vol. 5, no 11, 1806-1811 p.Article in journal (Refereed) Published
The relative position of L-a and L-b pi pi* electronic states in purine nucleobases is a much debated topic, since it can strongly affect our understanding of their photoexcited dynamics. To assess this point, we calculated the absorption and magnetic circular dichroism (MCD) spectra of adenine, guanine, and their nucleosides in gas-phase and aqueous solution,. exploiting recent developments in MCD computational technology within time-dependent density functional theory. MCD spectroscopy allows us to resolve the intense S-0 -greater than L-a transition from the weak S-0 -greater than L-b transition. The spectra obtained in water solution, by using B3LYP and CAM-B3LYP functionals and describing solvent effect by cluster models and by the polarizable continuum model (PCM), are in very good agreement with the experimental counterparts, thus providing direct and unambiguous evidence that the energy ordering predicted by TD-DFT, L-a less than L-b, is the correct one.
Place, publisher, year, edition, pages
American Chemical Society , 2014. Vol. 5, no 11, 1806-1811 p.
Engineering and Technology
IdentifiersURN: urn:nbn:se:liu:diva-108796DOI: 10.1021/jz500633tISI: 000337012500005OAI: oai:DiVA.org:liu-108796DiVA: diva2:732917