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Title: A deep UV trigger for ground-state ring-opening dynamics of 1,3-cyclohexadiene

Abstract

We explore the photo-induced kinetics of 1,3-cyclohexadiene upon excitation at 200 nm to the 3p state by ultrafast time-resolved, gas-phase x-ray scattering using the Linac Coherent Light Source. Analysis of the scattering anisotropy reveals that the excitation leads to the 3px and 3py Rydberg electronic states, which relax to the ground state with a time constant of 208 ± 11 fs. In contrast to the well-studied 266 nm excitation, at 200 nm the majority of the molecules (76 ± 3%) relax to vibrationally hot cyclohexadiene in the ground electronic state. A subsequent reaction on the ground electronic state surface leads from the hot cyclohexadiene to 1,3,5-hexatriene, with rates for the forward and backward reactions of 174 ± 13 and 355 ± 45 ps, respectively. The scattering pattern of the final hexatriene product reveals a thermal distribution of rotamers about the carbon-carbon single bonds.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3];  [3];  [4];  [4];  [4]; ORCiD logo [4];  [4]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]
  1. Brown Univ., Providence, RI (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
  2. Brown Univ., Providence, RI (United States)
  3. Univ. of Edinburgh, Scotland (United Kingdom)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
Brown Univ., Providence, RI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Royal Society of Edinburgh Sabbatical Fellowship; Carnegie Trust for the Universities of Scotland
Contributing Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
OSTI Identifier:
1596983
Grant/Contract Number:  
SC0017995; AC02-76SF00515; 58507; CRG050414
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 5; Journal Issue: 9; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ruddock, Jennifer M., Yong, Haiwang, Stankus, Brian, Du, Wenpeng, Goff, Nathan, Chang, Yu, Odate, Asami, Carrascosa, Andrés Moreno, Bellshaw, Darren, Zotev, Nikola, Liang, Mengning, Carbajo, Sergio, Koglin, Jason, Robinson, Joseph S., Boutet, Sébastien, Kirrander, Adam, Minitti, Michael P., and Weber, Peter M. A deep UV trigger for ground-state ring-opening dynamics of 1,3-cyclohexadiene. United States: N. p., 2019. Web. https://doi.org/10.1126/sciadv.aax6625.
Ruddock, Jennifer M., Yong, Haiwang, Stankus, Brian, Du, Wenpeng, Goff, Nathan, Chang, Yu, Odate, Asami, Carrascosa, Andrés Moreno, Bellshaw, Darren, Zotev, Nikola, Liang, Mengning, Carbajo, Sergio, Koglin, Jason, Robinson, Joseph S., Boutet, Sébastien, Kirrander, Adam, Minitti, Michael P., & Weber, Peter M. A deep UV trigger for ground-state ring-opening dynamics of 1,3-cyclohexadiene. United States. https://doi.org/10.1126/sciadv.aax6625
Ruddock, Jennifer M., Yong, Haiwang, Stankus, Brian, Du, Wenpeng, Goff, Nathan, Chang, Yu, Odate, Asami, Carrascosa, Andrés Moreno, Bellshaw, Darren, Zotev, Nikola, Liang, Mengning, Carbajo, Sergio, Koglin, Jason, Robinson, Joseph S., Boutet, Sébastien, Kirrander, Adam, Minitti, Michael P., and Weber, Peter M. Fri . "A deep UV trigger for ground-state ring-opening dynamics of 1,3-cyclohexadiene". United States. https://doi.org/10.1126/sciadv.aax6625. https://www.osti.gov/servlets/purl/1596983.
@article{osti_1596983,
title = {A deep UV trigger for ground-state ring-opening dynamics of 1,3-cyclohexadiene},
author = {Ruddock, Jennifer M. and Yong, Haiwang and Stankus, Brian and Du, Wenpeng and Goff, Nathan and Chang, Yu and Odate, Asami and Carrascosa, Andrés Moreno and Bellshaw, Darren and Zotev, Nikola and Liang, Mengning and Carbajo, Sergio and Koglin, Jason and Robinson, Joseph S. and Boutet, Sébastien and Kirrander, Adam and Minitti, Michael P. and Weber, Peter M.},
abstractNote = {We explore the photo-induced kinetics of 1,3-cyclohexadiene upon excitation at 200 nm to the 3p state by ultrafast time-resolved, gas-phase x-ray scattering using the Linac Coherent Light Source. Analysis of the scattering anisotropy reveals that the excitation leads to the 3px and 3py Rydberg electronic states, which relax to the ground state with a time constant of 208 ± 11 fs. In contrast to the well-studied 266 nm excitation, at 200 nm the majority of the molecules (76 ± 3%) relax to vibrationally hot cyclohexadiene in the ground electronic state. A subsequent reaction on the ground electronic state surface leads from the hot cyclohexadiene to 1,3,5-hexatriene, with rates for the forward and backward reactions of 174 ± 13 and 355 ± 45 ps, respectively. The scattering pattern of the final hexatriene product reveals a thermal distribution of rotamers about the carbon-carbon single bonds.},
doi = {10.1126/sciadv.aax6625},
journal = {Science Advances},
number = 9,
volume = 5,
place = {United States},
year = {2019},
month = {9}
}

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    Works referencing / citing this record:

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