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@PHDTHESIS{Walmsley:612494,
author = {Walmsley, Tiffany},
othercontributors = {Burt, Michael and Ritchie, Grant},
title = {{C}oulomb explosion imaging and covariance analysis of
concurrent fragmentation mechanisms},
school = {University of Oxford},
type = {Dissertation},
publisher = {University of Oxford},
reportid = {PUBDB-2024-05347},
pages = {256},
year = {2024},
note = {Dissertation, University of Oxford, 2024},
abstract = {This thesis uses Coulomb explosion imaging and covariance
analysis to characterise concurrent fragmentation processes
generating identical sets of products via different reaction
pathways, highlighting the potential of extending these
methods to study the photochemistry of larger, more
chemically relevant species than those that have previously
been studied. The photodissociation dynamics of CH2I2 at
202.5 nm were investigated using site-selective ionisation
at the I 4d orbitals using photons of 95 eV. A concerted
three-body dissociation process was assigned using charge
transfer features and time-dependent covariance. Dynamic
changes to the C-I internuclear distances and I-C-I bond
angle were characterised, demonstrating the potential of
Coulomb explosion imaging to simultaneously map potential
energy surfaces of reaction dynamics along multiple degrees
of freedom. Site-selective ionisation of 1- and
2-iodopropane at the I 4d orbitals was carried out using
photons of 95 eV. Modified three-dimensional momentum
covariance analysis techniques were used to disentangle
fragmentation processes generating the same sets of products
as well as the individual steps of multi-step fragmentation
mechanisms. Observable isomeric differences demonstrated the
sensitivity of individual fragmentation processes, and the
corresponding nuclear dynamics, to the geometry and charge
distribution of the parent polycation species. Iodobenzene
was site-selectively ionised at the I 4d orbitals using
photons of 120 eV, and valence-shell ionisation was also
conducted using 800 nm laser pulses. Covariance analysis
techniques were employed to analyse the range of products
generated from stable and metastable phenyl cations and
polycations, demonstrating how concurrent fragmentation
processes generating long-lived species in lowly-charged
cationic states can be characterised. Valence-shell
ionisation could initially ionise more atomic sites than
just iodine, leading to fragmentation channels that were not
observed with site-selective, inner-shell ionisation. Both
ionisation regimes generated similar sets of products but on
different relative timescales due to initially populating
different electronic excited states. Each ionisation regime
results in many observable fragmentation processes, but
photoelectron information is required to relate specific
fragmentation channels to specific ionisation and charge
generation/redistribution processes.},
keywords = {Chemistry, Physical and theoretical (Other)},
cin = {DOOR ; HAS-User},
cid = {I:(DE-H253)HAS-User-20120731},
pnm = {6G2 - FLASH (DESY) (POF4-6G2)},
pid = {G:(DE-HGF)POF4-6G2},
experiment = {EXP:(DE-H253)F-BL1-20150101},
typ = {PUB:(DE-HGF)11},
doi = {10.5287/ORA-Z6JGMXRRA},
url = {https://bib-pubdb1.desy.de/record/612494},
}