期刊
FARADAY DISCUSSIONS
卷 221, 期 -, 页码 202-218出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9fd00079h
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资金
- EPSRC [EP/L005646/1]
- Royal Society [SRF/R1/180079]
- Leverhulme Trust [SRF/R1/180079]
- Diamond Light Source [STU0157]
- EPSRC [EP/L005646/1] Funding Source: UKRI
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(1)pi pi* and 1(1)pi sigma* states of phenol, we observe 1(1)pi pi*-D-0/D-1 ionisation and competing direct S-0-D-0/D-1 ionisation. Following resonance-enhanced multiphoton ionisation via the 2(1)pi pi* 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.
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