Electron dynamics upon ionisation of polyatomic molecules: Coupling to quantum nuclear motion and decoherence
File(s)
Published version
Author(s)
Vacher, M
Bearpark, M
Robb, MA
Malhado, JP
Type
Journal Article
Abstract
Knowledge about the electronic motion in molecules is essential for our understanding of chemical
reactions and biological processes. The advent of attosecond techniques opens up the possibility to
induce electronic motion, observe it in real time and potentially steer it. A fundamental question
remains the factors influencing electronic decoherence and the role played by nuclear motion in this
process. Here, we simulate the dynamics upon ionisation of the polyatomic molecules para-xylene
and modified bismethylene-adamantane, with a quantum mechanical treatment of both electron and
nuclear dynamics using the direct dynamics variational multi-configuration Gaussian method. Our
simulations give new important physical insights about the expected decoherence process. We have
shown that the decoherence of electron dynamics happens on the time scale of a few femtoseconds,
with the interplay of different mechanisms: the
dephasing
is responsible for the fast decoherence
while the
nuclear overlap decay
may actually help maintaining it and is responsible for small revivals.
reactions and biological processes. The advent of attosecond techniques opens up the possibility to
induce electronic motion, observe it in real time and potentially steer it. A fundamental question
remains the factors influencing electronic decoherence and the role played by nuclear motion in this
process. Here, we simulate the dynamics upon ionisation of the polyatomic molecules para-xylene
and modified bismethylene-adamantane, with a quantum mechanical treatment of both electron and
nuclear dynamics using the direct dynamics variational multi-configuration Gaussian method. Our
simulations give new important physical insights about the expected decoherence process. We have
shown that the decoherence of electron dynamics happens on the time scale of a few femtoseconds,
with the interplay of different mechanisms: the
dephasing
is responsible for the fast decoherence
while the
nuclear overlap decay
may actually help maintaining it and is responsible for small revivals.
Date Issued
2017-02-23
Date Acceptance
2017-01-24
Citation
Physical Review Letters, 2017, 118 (8), pp.1-5
ISSN
1079-7114
Publisher
American Physical Society
Start Page
1
End Page
5
Journal / Book Title
Physical Review Letters
Volume
118
Issue
8
Copyright Statement
© 2017 The Authors. Published by the American Physical Society under the terms of
the Creative Commons Attribution 4.0 International license.
Further distribution of this work must maintain attribution to
the author(s) and the published article’s title, journal citation,
and DOI.
the Creative Commons Attribution 4.0 International license.
Further distribution of this work must maintain attribution to
the author(s) and the published article’s title, journal citation,
and DOI.
License URL
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Identifier
https://journals.aps.org/prl/abstract/10.1103/PhysRevLett.118.083001
Grant Number
EP/I032517/1
Subjects
Science & Technology
Physical Sciences
Physics, Multidisciplinary
Physics
HIGH HARMONIC-GENERATION
GAUSSIAN WAVEPACKETS
ATTOSECOND PULSES
TIME
MIGRATION
SYSTEMS
VMCG
Chemical Physics
Physical Chemistry
0307 Theoretical and Computational Chemistry
020201 Atomic and Molecular Physics
0306 Physical Chemistry (incl. Structural)
General Physics
01 Mathematical Sciences
02 Physical Sciences
09 Engineering
Publication Status
Published
Article Number
083001
Date Publish Online
2017-02-23