Ultrafast X-ray spectroscopy of conical intersections

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Bibliographic Details
Published in:Physical review letters Vol. 120; no. 24; p. 243001
Main Authors: Neville, Simon P, Chergui, Majed, Stolow, Albert, Schuurman, Michael S
Format: Journal Article
Language:English
Published: United States American Physical Society 12.06.2018
Subjects:
Chromophores
Dynamic structural analysis
Dynamics
Intersections
Localization
Spectrum analysis
X ray absorption
X ray sources
X ray spectra
X-ray spectroscopy
ISSN:0031-9007, 1079-7114, 1079-7114
Online Access:Get full text
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Summary:NRC publication: Yes
Ongoing developments in ultrafast x-ray sources offer powerful new means of probing the complex nonadiabatically coupled structural and electronic dynamics of photoexcited molecules. These non-Born-Oppenheimer effects are governed by general electronic degeneracies termed conical intersections, which play a key role, analogous to that of a transition state, in the electronic-nuclear dynamics of excited molecules. Using high-level ab initio quantum dynamics simulations, we studied time-resolved x-ray absorption (TRXAS) and photoelectron spectroscopy (TRXPS) of the prototypical unsaturated organic chromophore, ethylene, following excitation to its S2(ππ∗) state. The TRXAS, in particular, is highly sensitive to all aspects of the ensuing dynamics. These x-ray spectroscopies provide a clear signature of the wave packet dynamics near conical intersections, related to charge localization effects driven by the nuclear dynamics. Given the ubiquity of charge localization in excited state dynamics, we believe that ultrafast x-ray spectroscopies offer a unique and powerful route to the direct observation of dynamics around conical intersections.
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ISSN:0031-9007
1079-7114
1079-7114
DOI:10.1103/PhysRevLett.120.243001