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Tracking dissociation pathways of nitrobenzene via mega-electron-volt ultrafast electron diffraction

Journal Article · · Journal of Physics. B, Atomic, Molecular and Optical Physics
 [1];  [2];  [3];  [4];  [5];  [5];  [3];  [6];  [5];  [5];  [7];  [8];  [4]
  1. Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE); SLAC National Accelerator Laboratory
  2. Stanford Univ., CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE)
  3. Univ. of Nebraska, Lincoln, NE (United States)
  4. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Institute (PULSE)
  5. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
  6. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Diamond Light Source, Ltd.
  7. Tsinghua Univ., Beijing (China)
  8. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); University of Duisburg-Essen (Germany); Technical University of Dortmund (Germany); Research Alliance Ruhr (Germany)
+ Show Author Affiliations
As the simplest nitroaromatic compound, nitrobenzene is an interesting model system to explore the rich photochemistry of nitroaromatic compounds. Previous investigations of nitrobenzene's photochemical dynamics have probed structural and electronic properties. These investigations paint, at times, a convoluted and sometimes contradictory description of the photochemical landscape. Here, we investigate the ultrafast dynamics of nitrobenzene triggered by photoexcitation at 267 nm for the first time using a structural probe with femtosecond time resolution. Our probe complements previous measurements of nitrobenzene's electronic structure evolution and aids in determining the photochemical dynamics with less ambiguity. We employ megaelectronvolt ultrafast electron diffraction to follow nitrobenzene's structural evolution within the first 5 ps after photoexcitation. We observe ground state recovery within 160 ± 60 fs through nonadiabatic dynamics. Based on comparisons of the experimental signal with molecular dynamics simulations, we exclude a significant population of the triplet manifold. Furthermore, we do not observe fragmentation of nitrobenzene within the investigated time window, which indicates that previously observed photofragmentation reactions take place in the vibrationally 'hot' ground state on timescales considerably beyond 5 ps.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
AC02-05CH11231; AC02-76SF00515; SC0014170
OSTI ID:
2438088
Journal Information:
Journal of Physics. B, Atomic, Molecular and Optical Physics, Journal Name: Journal of Physics. B, Atomic, Molecular and Optical Physics Journal Issue: 19 Vol. 57; ISSN 0953-4075
Publisher:
IOP PublishingCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
excited state dynamics
ultrafast electron diffraction
ultrafast photochemistry