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Title: The photoexcitation of crystalline ice and amorphous solid water: A molecular dynamics study of outcomes at 11 K and 125 K

Abstract

Photoexcitation of crystalline ice Ih and amorphous solid water at 7-9 eV is examined using molecular dynamics simulations and a fully flexible water model. The probabilities of photofragment desorption, trapping, and recombination are examined for crystalline ice at 11 K and at 125 K and for amorphous solid water at 11 K. For 11 K crystalline ice, a fully rigid water model is also employed for comparison. The kinetic energy of desorbed H atoms and the distance travelled by trapped fragments are correlated to the location and the local environment of the photoexcited water molecule. In all cases, H atom desorption is found to be the most likely outcome in the top bilayer while trapping of all photofragments is most probable deeper in the solid where the likelihood for recombination of the fragments into H{sub 2}O molecules also rises. Trajectory analysis indicates that the local hydrogen bonding network in amorphous solid water is more easily distorted by a photodissociation event compared to crystalline ice. Also, simulations indicate that desorption of OH radicals and H{sub 2}O molecules are more probable in amorphous solid water. The kinetic energy distributions for desorbed H atoms show a peak at high energy in crystalline ice,more » arising from photoexcited water molecules in the top monolayer. This peak is less pronounced in amorphous solid water. H atoms that are trapped may be displaced by up to ∼10 water cages, but migrate on average 3 water cages. Trapped OH fragments tend to stay near the original solvent cage.« less

Authors:
; ;  [1]
  1. Department of Chemistry, Queen’s University, Kingston, Ontario K7L 3N6 (Canada)
Publication Date:
OSTI Identifier:
22490919
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 3; Other Information: (c) 2015 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; COMPARATIVE EVALUATIONS; DESORPTION; KINETIC ENERGY; MOLECULAR DYNAMICS METHOD; MOLECULES; PEAKS; PHOTOLYSIS; SIMULATION; SOLIDS; SOLVENTS; WATER

Citation Formats

Crouse, J., Loock, H.-P., E-mail: hploock@chem.queensu.ca, and Cann, N. M., E-mail: ncann@chem.queensu.ca. The photoexcitation of crystalline ice and amorphous solid water: A molecular dynamics study of outcomes at 11 K and 125 K. United States: N. p., 2015. Web. doi:10.1063/1.4926666.
Crouse, J., Loock, H.-P., E-mail: hploock@chem.queensu.ca, & Cann, N. M., E-mail: ncann@chem.queensu.ca. The photoexcitation of crystalline ice and amorphous solid water: A molecular dynamics study of outcomes at 11 K and 125 K. United States. doi:10.1063/1.4926666.
Crouse, J., Loock, H.-P., E-mail: hploock@chem.queensu.ca, and Cann, N. M., E-mail: ncann@chem.queensu.ca. Tue . "The photoexcitation of crystalline ice and amorphous solid water: A molecular dynamics study of outcomes at 11 K and 125 K". United States. doi:10.1063/1.4926666.
@article{osti_22490919,
title = {The photoexcitation of crystalline ice and amorphous solid water: A molecular dynamics study of outcomes at 11 K and 125 K},
author = {Crouse, J. and Loock, H.-P., E-mail: hploock@chem.queensu.ca and Cann, N. M., E-mail: ncann@chem.queensu.ca},
abstractNote = {Photoexcitation of crystalline ice Ih and amorphous solid water at 7-9 eV is examined using molecular dynamics simulations and a fully flexible water model. The probabilities of photofragment desorption, trapping, and recombination are examined for crystalline ice at 11 K and at 125 K and for amorphous solid water at 11 K. For 11 K crystalline ice, a fully rigid water model is also employed for comparison. The kinetic energy of desorbed H atoms and the distance travelled by trapped fragments are correlated to the location and the local environment of the photoexcited water molecule. In all cases, H atom desorption is found to be the most likely outcome in the top bilayer while trapping of all photofragments is most probable deeper in the solid where the likelihood for recombination of the fragments into H{sub 2}O molecules also rises. Trajectory analysis indicates that the local hydrogen bonding network in amorphous solid water is more easily distorted by a photodissociation event compared to crystalline ice. Also, simulations indicate that desorption of OH radicals and H{sub 2}O molecules are more probable in amorphous solid water. The kinetic energy distributions for desorbed H atoms show a peak at high energy in crystalline ice, arising from photoexcited water molecules in the top monolayer. This peak is less pronounced in amorphous solid water. H atoms that are trapped may be displaced by up to ∼10 water cages, but migrate on average 3 water cages. Trapped OH fragments tend to stay near the original solvent cage.},
doi = {10.1063/1.4926666},
journal = {Journal of Chemical Physics},
number = 3,
volume = 143,
place = {United States},
year = {Tue Jul 21 00:00:00 EDT 2015},
month = {Tue Jul 21 00:00:00 EDT 2015}
}
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