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An experimental and computational study of the effect of aqueous solution on the multiphoton ionisation photoelectron spectrum of phenol

Henley, A; Riley, J; Wang, B; Fielding, H; (2019) An experimental and computational study of the effect of aqueous solution on the multiphoton ionisation photoelectron spectrum of phenol. Faraday Discussions 10.1039/c9fd00079h. (In press). Green open access

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Abstract

We revisit the photoelectron spectroscopy of aqueous phenol in an effort to improve our understanding of the impact of inhomogeneous broadening and inelastic scattering on solution-phase photoelectron spectra. Following resonance-enhanced multiphoton ionisation via the 1 1ππ∗ and 1 1πσ∗ states of phenol, we observe 1 1ππ∗ -D0/D1 ionisation and competing direct S0-D0/D1 ionisation. Following resonance-enhanced multiphoton ionisation via the 2 1ππ∗ state, we observe the signature of solvated electrons. By comparing the photoelectron spectra of aqueous phenol with those of gas-phase phenol, we find that inelastic scattering results in peak shifts with similar values to those that have been observed in photoelectron spectra of solvated electrons, highlighting the need for a robust way of deconvoluting the effect of inelastic scattering from liquid-phase photoelectron spectra. We also present a computational strategy for calculating vertical ionisation energies using a quantum-mechanics/effective fragmentation potential (QM/EFP) approach in which we find that optimising the configurations obtained from molecular dynamics simulations and using the [phenol ·(H2O)5]QM[(H2O)n≥250]EFP (B3LYP/aug-cc-pvdz) method gives good agreement with experiment.

Type: Article
Title: An experimental and computational study of the effect of aqueous solution on the multiphoton ionisation photoelectron spectrum of phenol
Open access status: An open access version is available from UCL Discovery
DOI: 10.1039/c9fd00079h
Publisher version: https://doi.org/10.1039/c9fd00079h
Language: English
Additional information: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence https://creativecommons.org/licenses/by/3.0/
UCL classification: UCL > Provost and Vice Provost Offices
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: http://discovery.ucl.ac.uk/id/eprint/10080854
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