Imperial College London
Professor Michael Bearpark

ProfessorMichaelBearpark

Faculty of Natural Sciences, Department of Chemistry

Professor & Director of User Engagement
 
 
 
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Contact

 

+44 (0)20 7594 5727m.bearpark

 
 
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Location

 

110AMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Citation

BibTex format

@article{Vacher:2015:10.1103/PhysRevA.92.040502,
author = {Vacher, M and Steinberg, L and Jenkins, AJ and Bearpark, MJ and Robb, MA},
doi = {10.1103/PhysRevA.92.040502},
journal = {Physical Review A},
pages = {1--6},
title = {Electron dynamics following photoionization: decoherence due to the nuclear-wave-packet width},
url = {http://dx.doi.org/10.1103/PhysRevA.92.040502},
volume = {92},
year = {2015}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - The advent of attosecond techniques opens up the possibility to observe experimentally electron dynamics following ionization of molecules. Theoretical studies of pure electron dynamics at single fixed nuclear geometries in molecules have demonstrated oscillatory charge migration at a well-defined frequency but often neglecting the natural width of the nuclear wave packet. The effect on electron dynamics of the spatial delocalization of the nuclei is an outstanding question. Here, we show how the inherent distribution of nuclear geometries leads to dephasing. Using a simple analytical model, we demonstrate that the conditions for a long-lived electronic coherence are a narrow nuclear wave packet and almost parallel potential-energy surfaces of the states involved. We demonstrate with numerical simulations the decoherence of electron dynamics for two real molecular systems (paraxylene and polycyclic norbornadiene), which exhibit different decoherence time scales. To represent the quantum distribution of geometries of the nuclear wave packet, the Wigner distribution function is used. The electron dynamics decoherence result has significant implications for the interpretation of attosecond spectroscopy experiments since one no longer expects long-lived oscillations.
AU  - Vacher,M
AU  - Steinberg,L
AU  - Jenkins,AJ
AU  - Bearpark,MJ
AU  - Robb,MA
DO  - 10.1103/PhysRevA.92.040502
EP  - 6
PY  - 2015///
SN  - 1094-1622
SP  - 1
TI  - Electron dynamics following photoionization: decoherence due to the nuclear-wave-packet width
T2  - Physical Review A
UR  - http://dx.doi.org/10.1103/PhysRevA.92.040502
UR  - https://journals.aps.org/pra/abstract/10.1103/PhysRevA.92.040502
UR  - http://hdl.handle.net/10044/1/32354
VL  - 92
ER  -
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