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Title: Probing ground and low-lying excited states for HIO{sub 2} isomers

We present a computational study on HIO{sub 2} molecules. Ground state properties such as equilibrium structures, relative energetics, vibrational frequencies, and infrared intensities were obtained for all the isomers at the coupled-cluster with single and double excitations as well as perturbative inclusion of triples (CCSD(T)) level of theory with the aug-cc-pVTZ-PP basis set and ECP-28-PP effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. The HOIO structure is confirmed as the lowest energy isomer. The relative energies are shown to be HOIO < HOOI < HI(O)O. The HO(O)I isomer is only stable at the density functional theory (DFT) level of theory. The transition states determined show interconversion of the isomers is possible. In order to facilitate future experimental identification, vibrational frequencies are also determined for all corresponding deuterated species. Vertical excitation energies for the three lowest-lying singlet and triplet excited states were determined using the configuration interaction singles, time-dependent density functional theory (TD-DFT)/B3LYP, TD-DFT/G96PW91, and equation of motion-CCSD approaches with the LANL2DZ basis set plus effective core potential for iodine and the aug-cc-pVTZ basis set for hydrogen and oxygen atoms. It is shown that HOIO and HOOI isomers have excited states accessible at solarmore » wavelengths (<4.0 eV) but these states have very small oscillator strengths (<2 × 10{sup −3})« less
Authors:
 [1] ;  [2] ;  [3] ;  [4]
  1. Departamento de Química, Universidade Federal de Mato Grosso, Cuiabá, Mato Grosso 78060-900 (Brazil)
  2. (Brazil)
  3. (Canada)
  4. Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2 (Canada)
Publication Date:
OSTI Identifier:
22413334
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 23; 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; DENSITY FUNCTIONAL METHOD; EQUATIONS OF MOTION; EXCITED STATES; GROUND STATES; HYDROGEN; INCLUSIONS; IODINE; ISOMERS; MOLECULES; OXYGEN; TIME DEPENDENCE