On the multiphoton ionisation photoelectron spectra of phenol
On the multiphoton ionisation photoelectron spectra of phenol
The phenol molecule is a prototype for non-adiabatic dynamics and the excited-state photochemistry of biomolecules. In this article, we report a joint theoretical and experimental investigation on the resonance enhanced multiphoton ionisation photoelectron (REMPI) spectra of the two lowest ionisation bands of phenol. The focus is on the theoretical interpretation of the measured spectra using quantum dynamics simulations. These were performed by numerically solving the time-dependent Schrödinger equation using the multi-layer variant of the multiconfiguration time-dependent Hartree algorithm together with a vibronic coupling Hamiltonian model. The ionising laser pulse is modelled explicitly within the ionisation continuum model to simulate experimental femtosecond 1+1 REMPI photoelectron spectra. These measured spectra are sensitive to very short lived electronically excited states, providing a rigorous benchmark for our theoretical methods. The match between experiment and theory allows for an interpretation of the features of the spectra at different wavelengths and shows that there are features due to both ‘direct' and ‘indirect' ionisation, resulting from non-resonant and resonant excitation by the pump pulse.
3451–3461
Dey, Diptesh
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Woodhouse, Joanne L.
94d6c235-3e1e-44bc-8379-525862fd382c
Taylor, Marcus P.
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Fielding, Helen H.
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Worth, Graham A.
4460cae4-e70b-4cd7-9d07-119c86dd94cb
5 January 2025
Dey, Diptesh
df381644-f5d0-4aad-8cc5-6ed35d24674a
Woodhouse, Joanne L.
94d6c235-3e1e-44bc-8379-525862fd382c
Taylor, Marcus P.
aadb9a13-0a9c-452f-8d7e-47ff4b8fa6ca
Fielding, Helen H.
08a62947-4748-4638-ac7b-e829a42647a2
Worth, Graham A.
4460cae4-e70b-4cd7-9d07-119c86dd94cb
Dey, Diptesh, Woodhouse, Joanne L., Taylor, Marcus P., Fielding, Helen H. and Worth, Graham A.
(2025)
On the multiphoton ionisation photoelectron spectra of phenol.
Physical Chemistry Chemical Physics, 26 (4), .
(doi:10.1039/d3cp05559k).
Abstract
The phenol molecule is a prototype for non-adiabatic dynamics and the excited-state photochemistry of biomolecules. In this article, we report a joint theoretical and experimental investigation on the resonance enhanced multiphoton ionisation photoelectron (REMPI) spectra of the two lowest ionisation bands of phenol. The focus is on the theoretical interpretation of the measured spectra using quantum dynamics simulations. These were performed by numerically solving the time-dependent Schrödinger equation using the multi-layer variant of the multiconfiguration time-dependent Hartree algorithm together with a vibronic coupling Hamiltonian model. The ionising laser pulse is modelled explicitly within the ionisation continuum model to simulate experimental femtosecond 1+1 REMPI photoelectron spectra. These measured spectra are sensitive to very short lived electronically excited states, providing a rigorous benchmark for our theoretical methods. The match between experiment and theory allows for an interpretation of the features of the spectra at different wavelengths and shows that there are features due to both ‘direct' and ‘indirect' ionisation, resulting from non-resonant and resonant excitation by the pump pulse.
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d3cp05559k
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Accepted/In Press date: 3 January 2024
Published date: 5 January 2025
Additional Information:
Funding Information:
D. D. is thankful to Dr Michael Parkes for helpful discussions with ezDyson calculations. The research leading to these results has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie Grant agreement No. 892554 (D. D.), and the EPSRC under the COSMOS programme grant (EP/X026973/1) (G. W.). J. W. acknowledges funding from UCL, and M. T. from the University of Birmingham.
Publisher Copyright:
© 2024 The Royal Society of Chemistry
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Local EPrints ID: 486679
URI: http://eprints.soton.ac.uk/id/eprint/486679
ISSN: 1463-9076
PURE UUID: 0529891f-b214-4760-b24d-64b8c66dc4e6
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Date deposited: 01 Feb 2024 17:39
Last modified: 18 Apr 2024 01:56
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Contributors
Author:
Diptesh Dey
Author:
Joanne L. Woodhouse
Author:
Marcus P. Taylor
Author:
Helen H. Fielding
Author:
Graham A. Worth
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