Transient IR Spectroscopic Observation of Singlet and Triplet States of 2-Nitrofluorene: Revisiting the Photophysics of Nitroaromatics

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DOI

  • Martin A.B. Larsen, University of Copenhagen
  • ,
  • Jan Thøgersen
  • Anne B. Stephansen, University of Copenhagen, Denmark
  • Jorge Peón, Universidad Nacional Autónoma de México, Mexico
  • Theis I. Sølling, University of Copenhagen
  • ,
  • Søren Rud Keiding

The dynamics of 2-nitrofluorene (2-NF) in deuterated acetonitrile is studied using UV pump, IR probe femtosecond transient absorption spectroscopy. Upon excitation to the vibrationally excited S1 state, the excited state population of 2-NF branches into two different relaxation pathways. One route leads to intersystem crossing (ISC) to the triplet manifold within a few hundred femtoseconds and the other to internal conversion (IC) to the ground state. The experiments indicate that after relaxation to the energetic minimum on S1, 2-NF undergoes internal conversion to the ground state in about 15 ps. IC within the triplet manifold is also observed as the initially populated triplet state relaxes to T1 in about 6 ps. Rotational anisotropy measurements corroborate the assignment of the transient IR frequencies and indicate a rotational diffusion time of 2-NF in the solvent of about 14 ps. The combined set of results provides a unified picture of the dynamics in photoexcited 2-NF. This is to our knowledge the first example using femtosecond vibrational spectroscopy for the study of the fundamental photoinduced processes in nitroaromatic compounds.

Original languageEnglish
JournalJournal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume120
Issue1
Pages (from-to)28-35
Number of pages8
ISSN1089-5639
DOIs
Publication statusPublished - 2016

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