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Title: Diffractive imaging of dissociation and ground-state dynamics in a complex molecule

Abstract

We have investigated the structural dynamics in photoexcited 1,2-diiodotetrafluoroethane molecules $$(C_2F_4I_2)$$ in the gas phase experimentally using ultrafast electron diffraction and theoretically using FOMO-CASCI excited-state dynamics simulations. The molecules are excited by an ultraviolet femtosecond laser pulse to a state characterized by a transition from the iodine $5p⊥$ orbital to a mixed $5p ∥ σ$ hole and $$CF^∙_2$$ antibonding orbital, which results in the cleavage of one of the carbon-iodine bonds. We have observed, with sub-Angstrom resolution, the motion of the nuclear wave packet of the dissociating iodine atom followed by coherent vibrations in the electronic ground state of the $$C_2F_4I_2$$ radical. The radical reaches a stable classical (nonbridged) structure in less than 200 fs.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [7];  [7];  [7];  [4];  [1]
  1. Univ. of Nebraska, Lincoln, NE (United States). Dept. of Physics and Astronomy
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford PULSE Institute, Menlo Park CA (United States); Stanford Univ., CA (United States). Dept. of Chemistry
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford PULSE Institute, Menlo Park CA (United States)
  4. Stanford PULSE Institute, Menlo Park CA (United States)
  5. Univ. of Nebraska, Lincoln, NE (United States). Dept. of Physics and Astronomy; Univ. of York (United Kingdom). Dept. of Chemistry
  6. Stanford PULSE Institute, Menlo Park CA (United States); Univ. Potsdam, Potsdam (Germany). Inst. für Physik und Astronomie
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1560631
Alternate Identifier(s):
OSTI ID: 1546834
Grant/Contract Number:  
AC02-05-CH11231; AC02-76SF00515; SC0014170
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review A
Additional Journal Information:
Journal Volume: 100; Journal Issue: 2; Journal ID: ISSN 2469-9926
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Wilkin, Kyle J., Parrish, Robert M., Yang, Jie, Wolf, Thomas J. A., Nunes, J. Pedro F., Guehr, Markus, Li, Renkai, Shen, Xiaozhe, Zheng, Qiang, Wang, Xijie, Martinez, Todd J., and Centurion, Martin. Diffractive imaging of dissociation and ground-state dynamics in a complex molecule. United States: N. p., 2019. Web. doi:10.1103/physreva.100.023402.
Wilkin, Kyle J., Parrish, Robert M., Yang, Jie, Wolf, Thomas J. A., Nunes, J. Pedro F., Guehr, Markus, Li, Renkai, Shen, Xiaozhe, Zheng, Qiang, Wang, Xijie, Martinez, Todd J., & Centurion, Martin. Diffractive imaging of dissociation and ground-state dynamics in a complex molecule. United States. doi:10.1103/physreva.100.023402.
Wilkin, Kyle J., Parrish, Robert M., Yang, Jie, Wolf, Thomas J. A., Nunes, J. Pedro F., Guehr, Markus, Li, Renkai, Shen, Xiaozhe, Zheng, Qiang, Wang, Xijie, Martinez, Todd J., and Centurion, Martin. Fri . "Diffractive imaging of dissociation and ground-state dynamics in a complex molecule". United States. doi:10.1103/physreva.100.023402. https://www.osti.gov/servlets/purl/1560631.
@article{osti_1560631,
title = {Diffractive imaging of dissociation and ground-state dynamics in a complex molecule},
author = {Wilkin, Kyle J. and Parrish, Robert M. and Yang, Jie and Wolf, Thomas J. A. and Nunes, J. Pedro F. and Guehr, Markus and Li, Renkai and Shen, Xiaozhe and Zheng, Qiang and Wang, Xijie and Martinez, Todd J. and Centurion, Martin},
abstractNote = {We have investigated the structural dynamics in photoexcited 1,2-diiodotetrafluoroethane molecules $(C_2F_4I_2)$ in the gas phase experimentally using ultrafast electron diffraction and theoretically using FOMO-CASCI excited-state dynamics simulations. The molecules are excited by an ultraviolet femtosecond laser pulse to a state characterized by a transition from the iodine $5p⊥$ orbital to a mixed $5p ∥ σ$ hole and $CF^∙_2$ antibonding orbital, which results in the cleavage of one of the carbon-iodine bonds. We have observed, with sub-Angstrom resolution, the motion of the nuclear wave packet of the dissociating iodine atom followed by coherent vibrations in the electronic ground state of the $C_2F_4I_2$ radical. The radical reaches a stable classical (nonbridged) structure in less than 200 fs.},
doi = {10.1103/physreva.100.023402},
journal = {Physical Review A},
number = 2,
volume = 100,
place = {United States},
year = {2019},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Figures / Tables:

FIG. 1 FIG. 1: Weighted Legendre projection of the modified molecular scattering pattern ($sM$) for both experiment and simulations.

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