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Resonant multiphoton ionisation probe of the photodissociation dynamics of ammonia

Resonant multiphoton ionisation probe of the photodissociation dynamics of ammonia
Resonant multiphoton ionisation probe of the photodissociation dynamics of ammonia
The dissociation dynamics of the ?-state of ammonia have been studied using a resonant multiphoton ionisation probe in a photoelectron spectroscopy experiment. The use of a resonant intermediate in the multiphoton ionisation process changes the ionisation propensity, allowing access to different ion states when compared with equivalent single photon ionisation experiments. Ionisation through the E? 1A?1 Rydberg intermediate increases the observation window allowing us to monitor the excited state population for several hundred femtoseconds. The vibrational states in the photoelectron spectrum show two distinct timescales, 200 fs and 320 fs, that we assign to the non-adiabatic and adiabatic dissociation processes respectively. The different timescales derive from differences in the wavepacket trajectories for the two dissociation pathways that resonantly excite different vibrational states in the intermediate Rydberg state. The timescales are similar to those obtained from time resolved ion yield measurements, suggesting we can measure the different trajectories taken out to the region of conical intersection
1463-9076
1-7
Smith, Adam
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Watts, Hannah
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Jager, Edward
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Horke, Daniel
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Springate, Emma
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Alexander, Oliver
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Cacho, Cephise
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Chapman, Richard
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Minns, Russell
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Smith, Adam
af4cf6b6-1d87-47e7-a6f6-c8cc0ea20af8
Watts, Hannah
fac4dfc7-37ca-4ea7-93c1-33d0f774292f
Jager, Edward
a1d3594d-6c7b-4b1d-9575-130fc7406670
Horke, Daniel
ecebf884-717c-4948-a62b-0533d4e04aa3
Springate, Emma
8135f8ae-8d23-45d1-81f6-5bb6d901e304
Alexander, Oliver
eefa2701-8d3a-42cc-bf14-74a3e8b3622a
Cacho, Cephise
6104eeeb-9ac7-48a4-a03d-ec90b38f575a
Chapman, Richard
b696a894-6d7e-4ada-b9f9-994381a7d035
Minns, Russell
85280db4-c5a6-4a4c-82fe-75693c6a6045

Smith, Adam, Watts, Hannah, Jager, Edward, Horke, Daniel, Springate, Emma, Alexander, Oliver, Cacho, Cephise, Chapman, Richard and Minns, Russell (2016) Resonant multiphoton ionisation probe of the photodissociation dynamics of ammonia. Physical Chemistry Chemical Physics, 1-7. (doi:10.1039/C6CP05279G).

Record type: Article

Abstract

The dissociation dynamics of the ?-state of ammonia have been studied using a resonant multiphoton ionisation probe in a photoelectron spectroscopy experiment. The use of a resonant intermediate in the multiphoton ionisation process changes the ionisation propensity, allowing access to different ion states when compared with equivalent single photon ionisation experiments. Ionisation through the E? 1A?1 Rydberg intermediate increases the observation window allowing us to monitor the excited state population for several hundred femtoseconds. The vibrational states in the photoelectron spectrum show two distinct timescales, 200 fs and 320 fs, that we assign to the non-adiabatic and adiabatic dissociation processes respectively. The different timescales derive from differences in the wavepacket trajectories for the two dissociation pathways that resonantly excite different vibrational states in the intermediate Rydberg state. The timescales are similar to those obtained from time resolved ion yield measurements, suggesting we can measure the different trajectories taken out to the region of conical intersection

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C6CP05279G.pdf - Accepted Manuscript
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Accepted/In Press date: 14 September 2016
e-pub ahead of print date: 16 September 2016
Organisations: Computational Systems Chemistry

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Local EPrints ID: 400526
URI: http://eprints.soton.ac.uk/id/eprint/400526
ISSN: 1463-9076
PURE UUID: 9b3e3468-b2e8-4a21-9ee6-985f7e2269b1
ORCID for Russell Minns: ORCID iD orcid.org/0000-0001-6775-2977

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Date deposited: 19 Sep 2016 10:14
Last modified: 15 Mar 2024 05:53

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Contributors

Author: Adam Smith
Author: Hannah Watts
Author: Edward Jager
Author: Daniel Horke
Author: Emma Springate
Author: Oliver Alexander
Author: Cephise Cacho
Author: Richard Chapman
Author: Russell Minns ORCID iD

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