Reliable Potential Energy Surfaces for the Reactions of H2O with ThO2, PaO2+, UO22+, and UO2+
Abstract
The potential energy surfaces for the reactions of H2O with ThO2, PaO2+, UO22+, and UO2+ have been calculated at the coupled cluster CCSD(T) level extrapolated to the complete basis set limit with additional corrections including scalar relativistic and spin-orbit. The reactions proceed by the formation of an initial Lewis acid-base adduct (H2O)AnO20/+/2+ followed by a proton transfer to generate the dihydroxide AnO(OH)20/+/2+. The results are in excellent agreement with mass spectrometry experiments and prior calculations of hydrolysis reactions of the group 4 transition metal dioxides MO2. The differences in the energies of the stationary points on the potential energy surface are explained in terms of the charges on the system and the populations on the metal center. The use of an improved starting point for the coupled cluster CCSD(T) calculations based on density functional theory with the PW91 exchange-correlation functional or Brueckner orbitals is described. The importance of including second-order spin-orbit corrections for closed-shell molecules is also described. These improvements in the calculations are then correlated with the 5f populations on the actinide.
- Authors:
-
- Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry
- Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1461097
- Grant/Contract Number:
- AC02-05CH11231; FG02-12ER16329
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 119; Journal Issue: 46; Related Information: © 2015 American Chemical Society.; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; actinyl reactions; coupled cluster CCSD(T); relativistic quantum chemistry; hydrolysis
Citation Formats
Vasiliu, Monica, Peterson, Kirk A., Gibson, John K., and Dixon, David A. Reliable Potential Energy Surfaces for the Reactions of H2O with ThO2, PaO2+, UO22+, and UO2+. United States: N. p., 2015.
Web. doi:10.1021/acs.jpca.5b08618.
Vasiliu, Monica, Peterson, Kirk A., Gibson, John K., & Dixon, David A. Reliable Potential Energy Surfaces for the Reactions of H2O with ThO2, PaO2+, UO22+, and UO2+. United States. https://doi.org/10.1021/acs.jpca.5b08618
Vasiliu, Monica, Peterson, Kirk A., Gibson, John K., and Dixon, David A. Wed .
"Reliable Potential Energy Surfaces for the Reactions of H2O with ThO2, PaO2+, UO22+, and UO2+". United States. https://doi.org/10.1021/acs.jpca.5b08618. https://www.osti.gov/servlets/purl/1461097.
@article{osti_1461097,
title = {Reliable Potential Energy Surfaces for the Reactions of H2O with ThO2, PaO2+, UO22+, and UO2+},
author = {Vasiliu, Monica and Peterson, Kirk A. and Gibson, John K. and Dixon, David A.},
abstractNote = {The potential energy surfaces for the reactions of H2O with ThO2, PaO2+, UO22+, and UO2+ have been calculated at the coupled cluster CCSD(T) level extrapolated to the complete basis set limit with additional corrections including scalar relativistic and spin-orbit. The reactions proceed by the formation of an initial Lewis acid-base adduct (H2O)AnO20/+/2+ followed by a proton transfer to generate the dihydroxide AnO(OH)20/+/2+. The results are in excellent agreement with mass spectrometry experiments and prior calculations of hydrolysis reactions of the group 4 transition metal dioxides MO2. The differences in the energies of the stationary points on the potential energy surface are explained in terms of the charges on the system and the populations on the metal center. The use of an improved starting point for the coupled cluster CCSD(T) calculations based on density functional theory with the PW91 exchange-correlation functional or Brueckner orbitals is described. The importance of including second-order spin-orbit corrections for closed-shell molecules is also described. These improvements in the calculations are then correlated with the 5f populations on the actinide.},
doi = {10.1021/acs.jpca.5b08618},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 46,
volume = 119,
place = {United States},
year = {Wed Oct 28 00:00:00 EDT 2015},
month = {Wed Oct 28 00:00:00 EDT 2015}
}
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