Nuclear spatial delocalization silences electron density oscillations in 2-phenyl-ethyl-amine (PEA) and 2-phenylethyl-N,N-dimethylamine (PENNA) cations
File(s)
Published version
Author(s)
Jenkins, AJ
Vacher, M
Bearpark, MJ
Robb, MA
Type
Journal Article
Abstract
We simulate electron dynamics following ionization in 2-phenyl-ethyl-amine and 2-phenylethyl-N,N-dimethylamine as examples of systems where 3 coupled cationic states are involved. We study two nuclear effects on electron dynamics: (i) coupled electron-nuclear motion and (ii) nuclear spatial delocalization as a result of the zero-point energy in the neutral molecule. Within the Ehrenfest approximation, our calculations show that the coherent electron dynamics in these molecules is not lost as a result of coupled electron-nuclear motion. In contrast, as a result of nuclear spatial delocalization, dephasing of the oscillations occurs on a time scale of only a few fs, long before any significant nuclear motion can occur. The results have been rationalized using a semi-quantitative model based upon the gradients of the potential energy surfaces.
Date Issued
2016-03-14
Date Acceptance
2016-02-23
Citation
Journal of Chemical Physics, 2016, 144 (10)
ISSN
1089-7690
Publisher
American Institute of Physics (AIP)
Journal / Book Title
Journal of Chemical Physics
Volume
144
Issue
10
Copyright Statement
© 2016 AIP Publishing LLC. The following article appeared in The Journal of Chemical Physics, Volume 144, Issue 10, and may be found at http://dx.doi.org/10.1063/1.4943273
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/I032517/1
Subjects
Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
ULTRAFAST CHARGE MIGRATION
COVALENT EXCITED-STATES
IONIZATION
DYNAMICS
PEPTIDES
GEOMETRY
PULSES
Chemical Physics
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Publication Status
Published
Article Number
104110