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Photo-induced structural dynamics of o-nitrophenol by ultrafast electron diffraction

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/d3cp06253h· OSTI ID:2352482
 [1];  [2];  [3];  [4];  [5];  [2];  [6];  [6];  [4];  [4];  [2];  [4];  [4];  [2];  [7];  [6]
  1. University of Nebraska, Lincoln, NE (United States); University of Nebraska - Lincoln
  2. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Stanford University, CA (United States)
  3. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Tsinghua University, Beijing (China)
  4. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
  5. Newcastle University, Newcastle upon Tyne (United Kingdom)
  6. University of Nebraska, Lincoln, NE (United States)
  7. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Universität Duisburg Essen, Bochum (Germany); Technische Universität Dortmund, Bochum (Germany)
+ Show Author Affiliations
The photo-induced dynamics of o-nitrophenol, particularly its photolysis, has garnered significant scientific interest as a potential source of nitrous acid in the atmosphere. Although the photolysis products and preceding photo-induced electronic structure dynamics have been investigated extensively, the nuclear dynamics accompanying the non-radiative relaxation of o-nitrophenol on the ultrafast timescale, which include an intramolecular proton transfer step, have not been experimentally resolved. Herein, we present a direct observation of the ultrafast nuclear motions mediating photo-relaxation using ultrafast electron diffraction. Here, this work spatiotemporally resolves the loss of planarity which enables access to a conical intersection between the first excited state and the ground state after the proton transfer step, on the femtosecond timescale and with sub-Angstrom resolution. Our observations, supported by ab initio multiple spawning simulations, provide new insights into the proton transfer mediated relaxation mechanism in o-nitrophenol.
Research Organization:
University of Nebraska, Lincoln, NE (United States)
Sponsoring Organization:
USDOE; 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:
2352482
Alternate ID(s):
OSTI ID: 2352328
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 26 Vol. 26; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
femtosecond
molecular dynamics
proton transfer
structural dynamics
ultrafast electron diffraction