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Title: Communication: Oscillating charge migration between lone pairs persists without significant interaction with nuclear motion in the glycine and Gly-Gly-NH-CH{sub 3} radical cations

Abstract

Coupled electron-nuclear dynamics has been studied, using the Ehrenfest method, for four conformations of the glycine molecule and a single conformation of Gly-Gly-NH-CH{sub 3}. The initial electronic wavepacket was a superposition of eigenstates corresponding to ionization from the σ lone pairs associated with the carbonyl oxygens and the amine nitrogen. For glycine, oscillating charge migration (when the nuclei were frozen) was observed for the 4 conformers studied with periods ranging from 2 to 5 fs, depending on the energy gap between the lone pair cationic states. When coupled nuclear motion was allowed (which was mainly NH{sub 2} partial inversion), the oscillations hardly changed. For Gly-Gly-NH-CH{sub 3}, charge migration between the carbonyl oxygens and the NH{sub 2} lone pair can be observed with a period similar to glycine itself, also without interaction with nuclear motion. These simulations suggest that charge migration between lone pairs can occur independently of the nuclear motion.

Authors:
; ;  [1]
  1. Department of Chemistry, Imperial College London, London SW7 2AZ (United Kingdom)
Publication Date:
OSTI Identifier:
22304360
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 20; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMINES; CARBONYLS; CATIONS; EIGENSTATES; ELECTRONS; ENERGY GAP; GLYCINE; INTERACTIONS; MOLECULES; NITROGEN; NUCLEI; OSCILLATIONS; OXYGEN; RADICALS; SIMULATION; WAVE PACKETS

Citation Formats

Vacher, Morgane, Bearpark, Michael J., and Robb, Michael A. Communication: Oscillating charge migration between lone pairs persists without significant interaction with nuclear motion in the glycine and Gly-Gly-NH-CH{sub 3} radical cations. United States: N. p., 2014. Web. doi:10.1063/1.4879516.
Vacher, Morgane, Bearpark, Michael J., & Robb, Michael A. Communication: Oscillating charge migration between lone pairs persists without significant interaction with nuclear motion in the glycine and Gly-Gly-NH-CH{sub 3} radical cations. United States. doi:10.1063/1.4879516.
Vacher, Morgane, Bearpark, Michael J., and Robb, Michael A. Wed . "Communication: Oscillating charge migration between lone pairs persists without significant interaction with nuclear motion in the glycine and Gly-Gly-NH-CH{sub 3} radical cations". United States. doi:10.1063/1.4879516.
@article{osti_22304360,
title = {Communication: Oscillating charge migration between lone pairs persists without significant interaction with nuclear motion in the glycine and Gly-Gly-NH-CH{sub 3} radical cations},
author = {Vacher, Morgane and Bearpark, Michael J. and Robb, Michael A.},
abstractNote = {Coupled electron-nuclear dynamics has been studied, using the Ehrenfest method, for four conformations of the glycine molecule and a single conformation of Gly-Gly-NH-CH{sub 3}. The initial electronic wavepacket was a superposition of eigenstates corresponding to ionization from the σ lone pairs associated with the carbonyl oxygens and the amine nitrogen. For glycine, oscillating charge migration (when the nuclei were frozen) was observed for the 4 conformers studied with periods ranging from 2 to 5 fs, depending on the energy gap between the lone pair cationic states. When coupled nuclear motion was allowed (which was mainly NH{sub 2} partial inversion), the oscillations hardly changed. For Gly-Gly-NH-CH{sub 3}, charge migration between the carbonyl oxygens and the NH{sub 2} lone pair can be observed with a period similar to glycine itself, also without interaction with nuclear motion. These simulations suggest that charge migration between lone pairs can occur independently of the nuclear motion.},
doi = {10.1063/1.4879516},
journal = {Journal of Chemical Physics},
number = 20,
volume = 140,
place = {United States},
year = {Wed May 28 00:00:00 EDT 2014},
month = {Wed May 28 00:00:00 EDT 2014}
}