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

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.

doi:10.1126/sciadv.aax6625

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

Journal Article · Fri Sep 06 04:00:00 EDT 2019 · Science Advances

DOI:https://doi.org/10.1126/sciadv.aax6625· OSTI ID:1596983

^[1]; ^[2]; Stankus, Brian ^[2]; ^[2]; Goff, Nathan ^[2]; ^[2]; ^[2]; ^[3]; Bellshaw, Darren ^[3]; Zotev, Nikola ^[4]; Liang, Mengning ^[4]; Carbajo, Sergio ^[4]; ^[4]; Robinson, Joseph S. ^[4]; ^[4]; ^[3]; ^[4]; ^[2]

Brown Univ., Providence, RI (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Brown University
Brown Univ., Providence, RI (United States)
Univ. of Edinburgh, Scotland (United Kingdom)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Brown Univ., Providence, RI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; Royal Society of Edinburgh Sabbatical Fellowship; Carnegie Trust for the Universities of Scotland

Contributing Organization:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Grant/Contract Number:: SC0017995; AC02-76SF00515

OSTI ID:: 1596983

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 9 Vol. 5; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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