@phdthesis{discovery10204282,
           month = {January},
           title = {Photodetachment from phenolate in vacuo and in aqueous solution},
            note = {Copyright {\copyright} The Author 2025.  Original content in this thesis is licensed under the terms of the Creative Commons Attribution-NonCommercial 4.0 International (CC BY-NC 4.0) Licence (https://creativecommons.org/licenses/by-nc/4.0/).  Any third-party copyright material present remains the property of its respective owner(s) and is licensed under its existing terms.  Access may initially be restricted at the author's request.},
           pages = {1--212},
            year = {2025},
          school = {UCL (University College London)},
          author = {Fortune, William George},
             url = {https://discovery.ucl.ac.uk/id/eprint/10204282/},
        abstract = {This thesis explores the use of two experimental techniques, gas-phase anion
photoelectron spectroscopy, and liquid microjet photoelectron spectroscopy, to
investigate the electronic structure, excited state dynamics and photodetachment
mechanisms in the phenolate anion. The experimental work focuses on the role of
both the absence, and the inclusion, of a native environment and the ways in which
the environment affects the electronic properties of the phenolate anion across the
use of both experimental techniques.
Chapter 1 details a background to the electronic structure of both isolated and
solvated molecular anions. It also describes photoelectron spectroscopy in both the
gas-phase and solution phase, and discusses any experimental considerations when
conducting such experiments. An introduction to the phenolate anion as a molecular
motif is also presented.
Chapter 2 will introduce the experimental apparatus for both the nanosecond
anion photoelectron spectrometer, and the liquid microjet photoelectron spectrometer.
This chapter will also address the data processing methods used in this work.
Chapter 3 presents gas-phase photodetachment spectra of the isolated phenolate
anion, which is a common motif in both the green fluorescent protein and the
photoactive yellow protein. The photodetachment spectra are presented alongside
photoelectron angular distributions, to examine both direct detachment channels and resonant excitation to the S1 ( {\ensuremath{\pi}}{\ensuremath{\pi}}*) state in the range 300-370 nm. Subsequently,
a room-temperature photodetachment action spectrum, which examines
the absorption processes in isolated phenolate between 300-600 nm, is presented.
In chapter 4, the phenolate anion is examined using liquid-microjet photoelectron
spectroscopy, over the range 236-300 nm. This work examines both resonant
{\ensuremath{\pi}}-{\ensuremath{\pi}}* transitions to the first two singlet excited states, exploring resonance-
enhanced multiphoton detachment. This chapter also benchmarks the non-resonant
two-photon binding energy in phenolate using UV photons. Photoelectron spectra
presented in this chapter have been included work published in the literature,
supporting transient absorption spectroscopy measurements and assisting the advancement
of work on electron scattering in solutions.
Chapter 5 will provide a summary of the work presented in this thesis and discusses
current and future experimental work which would supplement this research
area.}
}