Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction

Andrew R Attar; Aditi Bhattacherjee; C D Pemmaraju; Kirsten Schnorr; Kristina D Closser; David Prendergast; Stephen R Leone

doi:10.1126/science.aaj2198

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Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction

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Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction

Andrew R Attar, Aditi Bhattacherjee, C D Pemmaraju, Kirsten Schnorr, Kristina D Closser, David Prendergast and Stephen R Leone

Science (American Association for the Advancement of Science), Vol.356(6333), pp.54-59

04/07/2017

DOI: 10.1126/science.aaj2198

PMID: 28386006

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Abstract

The ultrafast light-activated electrocyclic ring-opening reaction of 1,3-cyclohexadiene is a fundamental prototype of photochemical pericyclic reactions. Generally, these reactions are thought to proceed through an intermediate excited-state minimum (the so-called pericyclic minimum), which leads to isomerization via nonadiabatic relaxation to the ground state of the photoproduct. Here, we used femtosecond (fs) soft x-ray spectroscopy near the carbon K-edge (~284 electron volts) on a tabletop apparatus to directly reveal the valence electronic structure of this transient intermediate state. The core-to-valence spectroscopic signature of the pericyclic minimum observed in the experiment was characterized, in combination with time-dependent density functional theory calculations, to reveal overlap and mixing of the frontier valence orbital energy levels. We show that this transient valence electronic structure arises within 60 ± 20 fs after ultraviolet photoexcitation and decays with a time constant of 110 ± 60 fs.

Details

Title: Subtitle: Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction
Creators: Andrew R Attar - Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Aditi Bhattacherjee - Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
C D Pemmaraju - Theory Institute for Materials and Energy Spectroscopies, SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA
Kirsten Schnorr - Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Kristina D Closser - The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
David Prendergast - The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Stephen R Leone - Department of Physics, University of California, Berkeley, CA 94720, USA
Resource Type: Journal article
Publication Details: Science (American Association for the Advancement of Science), Vol.356(6333), pp.54-59
DOI: 10.1126/science.aaj2198
PMID: 28386006
NLM abbreviation: Science
ISSN: 0036-8075
eISSN: 1095-9203
Grant note: DOI: 10.13039/100000001, name: National Science Foundation, award: award299191, EEC-0310717; DOI: 10.13039/100000015, name: U.S. Department of Energy, award: award299187, DE-AC02-05CH11231; DOI: 10.13039/100000015, name: U.S. Department of Energy, award: award302135, DE-AC02-76SF00515
Language: English
Date published: 04/07/2017
Academic Unit: Chemistry
Record Identifier: 9984216587602771

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