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Excited state dynamics of CH2I2 and CH2BrI studied with UV pump VUV probe photoelectron spectroscopy

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.5086665· OSTI ID:1609963
 [1];  [2];  [3];  [4];  [5];  [6];  [5];  [7];  [8];  [2]
  1. Stony Brook Univ., NY (United States). Dept. of Physics and Astronomy; DOE/OSTI
  2. Stony Brook Univ., NY (United States). Dept. of Physics and Astronomy
  3. Univ. of Ottawa, ON (Canada). Dept. of Physics; Univ. College London, Bloomsbury (United Kingdom)
  4. Univ. of Ottawa, ON (Canada). Dept. of Physics
  5. National Research Council of Canada, Ottawa, ON (Canada)
  6. Univ. of Ottawa, ON (Canada). Dept. of Physics; National Research Council of Canada, Ottawa, ON (Canada); Univ., of Ottawa, ON (Canada). Dept. of Chemistry
  7. Univ. of Vienna, Wien (Austria). Inst. of Theoretical Chemistry
  8. Hungarian Academy of Sciences, Budapest (Hungary). Research Centre for Natural Sciences and Wigner Research Centre for Physics
+ Show Author Affiliations
We compare the excited state dynamics of diiodomethane (CH2I2) and bromoiodomethane (CH2BrI) using time resolved photoelectron spectroscopy. A 4.65 eV UV pump pulse launches a dissociative wave packet on excited states of both molecules and the ensuing dynamics are probed via photoionization using a 7.75 eV probe pulse. The resulting photoelectrons are measured with the velocity map imaging technique for each pump-probe delay. Our measurements highlight differences in the dynamics for the two molecules, which are interpreted with high-level ab initio molecular dynamics (trajectory surface hopping) calculations. Our analysis allows us to associate features in the photoelectron spectrum with different portions of the excited state wave packet represented by different trajectories. The excited state dynamics in bromoiodomethane are simple and can be described in terms of direct dissociation along the C–I coordinate, whereas the dynamics in diiodomethane involve internal conversion and motion along multiple dimensions.
Research Organization:
State Univ. of New York (SUNY), Albany, NY (United States)
Sponsoring Organization:
Engineering and Physical Sciences Research Council (EPSRC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-08ER15984
OSTI ID:
1609963
Alternate ID(s):
OSTI ID: 1511081
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 17 Vol. 150; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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