Non-adiabatic intramolecular and photodissociation dynamics studied by femtosecond time-resolved photoelectron and coincidence imaging spectroscopy

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DOIResolve DOI: http://doi.org/10.1039/b316742a
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TypeArticle
Journal titleFaraday Discussions
ISSN13596640
Volume127
Pages193212; # of pages: 20
AbstractTime-resolved photoelectron spectroscopy (TRPES) is emerging as a useful tool for the study of non-adiabatic dynamics in isolated polyatomic molecules and clusters due to its sensitivity to both electronic and vibrational dynamics. A powerful extension of TRPES, coincidence imaging spectroscopy (CIS), based upon femtosecond time-resolved 3D momentum vector imaging of both photoions and photoelectrons in coincidence, is a new technique for the study of complex dissociative processes. Here we show how these spectroscopies can be used to study both non-adiabatic intramolecular and photodissociation dynamics in polyatomic molecules. Intramolecular dynamics in the [small alpha],[small beta]-enones acrolein, crotonaldehyde and methyl vinyl ketone are studied using both TRPES and laser-induced fluorescence of HCO(X) product yields. The location of the methyl group is seen to have very dramatic effects on the relative electronic relaxation rates and the HCO(X) yield. Applying both TRPES and CIS to the 200 nm and 209 nm photodissociation of the nitric oxide dimer, (NO)2, we observe the fs time-scale evolution of the excited parent neutral via its photoelectron spectrum and the emergence of the NO(A) photofragment including its energy and angular distributions.
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AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedNo
NPARC number12327991
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Record identifier4d3f63c3-b6f6-42f0-87b8-43ee6484cd05
Record created2009-09-10
Record modified2016-05-09
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