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Title: Calculated vibrational states of ozone up to dissociation

A new accurate global potential energy surface for the ground electronic state of ozone [R. Dawes et al., J. Chem. Phys. 139, 201103 (2013)] was published fairly recently. The topography near dissociation differs significantly from previous surfaces, without spurious submerged reefs and corresponding van der Waals wells. This has enabled significantly improved descriptions of scattering processes, capturing the negative temperature dependence and large kinetic isotope effects in exchange reaction rates. The exchange reactivity was found to depend on the character of near-threshold resonances and their overlap with reactant and product wavefunctions, which in turn are sensitive to the potential. We present global “three-well” calculations of all bound vibrational states of three isotopic combinations of ozone ( 48O 3, 16O 2 18O, 16O 2 17O) for J = 0 and J = 1 with a focus on the character and density of highly excited states and discuss their impact on the ozone isotopic anomaly. The calculations were done using a parallel symmetry-adapted Lanczos method with the RV3 code. Some comparisons were made with results obtained with the improved relaxation method implemented in the Heidelberg multi-configuration time-dependent Hartree code.
Authors:
 [1] ;  [1] ;  [2] ; ORCiD logo [2] ; ORCiD logo [3] ;  [4]
  1. Missouri Univ. of Science and Technology, Rolla, MO (United States). Dept. of Chemistry
  2. Queen's Univ., Kingston, ON (Canada). Dept. of Chemistry
  3. Chinese Academy of Sciences (CAS), Dalian (China). Dalian Inst. of Chemical Physics, State Key Lab. of Molecular Reaction Dynamics and Center for Theoretical and Computational Chemistry; Univ. of Science and Technology of China, Hefei (China). Center for Advanced Chemical Physics and Frontier Center for Quantum Science and Technology
  4. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
Publication Date:
Grant/Contract Number:
FG02-05ER15694; CHE-1300945; 2013CB922200; 21222308; 21103187; 21133006
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); Natural Sciences and Engineering Research Council of Canada (NSERC); National Basic Research Program of China; National Natural Science Foundation of China (NNSFC); Chinese Academy of Sciences (CAS)
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; exchange reactions; algorithms and data structure; vibrational states; temperature coefficient; chemical elements; air pollution; Hamiltonian mechanics; kinetic isotope effects; potential energy surfaces; relaxation method
OSTI Identifier:
1469307
Alternate Identifier(s):
OSTI ID: 1238207

Ndengué, Steve, Dawes, Richard, Wang, Xiao-Gang, Carrington, Tucker, Sun, Zhigang, and Guo, Hua. Calculated vibrational states of ozone up to dissociation. United States: N. p., Web. doi:10.1063/1.4941559.
Ndengué, Steve, Dawes, Richard, Wang, Xiao-Gang, Carrington, Tucker, Sun, Zhigang, & Guo, Hua. Calculated vibrational states of ozone up to dissociation. United States. doi:10.1063/1.4941559.
Ndengué, Steve, Dawes, Richard, Wang, Xiao-Gang, Carrington, Tucker, Sun, Zhigang, and Guo, Hua. 2016. "Calculated vibrational states of ozone up to dissociation". United States. doi:10.1063/1.4941559. https://www.osti.gov/servlets/purl/1469307.
@article{osti_1469307,
title = {Calculated vibrational states of ozone up to dissociation},
author = {Ndengué, Steve and Dawes, Richard and Wang, Xiao-Gang and Carrington, Tucker and Sun, Zhigang and Guo, Hua},
abstractNote = {A new accurate global potential energy surface for the ground electronic state of ozone [R. Dawes et al., J. Chem. Phys. 139, 201103 (2013)] was published fairly recently. The topography near dissociation differs significantly from previous surfaces, without spurious submerged reefs and corresponding van der Waals wells. This has enabled significantly improved descriptions of scattering processes, capturing the negative temperature dependence and large kinetic isotope effects in exchange reaction rates. The exchange reactivity was found to depend on the character of near-threshold resonances and their overlap with reactant and product wavefunctions, which in turn are sensitive to the potential. We present global “three-well” calculations of all bound vibrational states of three isotopic combinations of ozone (48O3, 16O218O, 16O217O) for J = 0 and J = 1 with a focus on the character and density of highly excited states and discuss their impact on the ozone isotopic anomaly. The calculations were done using a parallel symmetry-adapted Lanczos method with the RV3 code. Some comparisons were made with results obtained with the improved relaxation method implemented in the Heidelberg multi-configuration time-dependent Hartree code.},
doi = {10.1063/1.4941559},
journal = {Journal of Chemical Physics},
number = 7,
volume = 144,
place = {United States},
year = {2016},
month = {2}
}