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Title: Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes

Authors:
 [1];  [2];  [3];  [3];  [3]; ORCiD logo [2]; ORCiD logo [4]
  1. Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States
  2. Department of Chemistry, University of Minnesota, Superconducting Institute, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
  3. Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, Indiana 46556, United States
  4. Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States; Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, Indiana 46556, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388539
DOE Contract Number:
SC0001089
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 56; Journal Issue: 3; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory
Country of Publication:
United States
Language:
English
Subject:
nuclear (including radiation effects), materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Dembowski, Mateusz, Bernales, Varinia, Qiu, Jie, Hickam, Sarah, Gaspar, Gabriel, Gagliardi, Laura, and Burns, Peter C. Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.6b02666.
Dembowski, Mateusz, Bernales, Varinia, Qiu, Jie, Hickam, Sarah, Gaspar, Gabriel, Gagliardi, Laura, & Burns, Peter C. Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes. United States. doi:10.1021/acs.inorgchem.6b02666.
Dembowski, Mateusz, Bernales, Varinia, Qiu, Jie, Hickam, Sarah, Gaspar, Gabriel, Gagliardi, Laura, and Burns, Peter C. Wed . "Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes". United States. doi:10.1021/acs.inorgchem.6b02666.
@article{osti_1388539,
title = {Computationally-Guided Assignment of Unexpected Signals in the Raman Spectra of Uranyl Triperoxide Complexes},
author = {Dembowski, Mateusz and Bernales, Varinia and Qiu, Jie and Hickam, Sarah and Gaspar, Gabriel and Gagliardi, Laura and Burns, Peter C.},
abstractNote = {},
doi = {10.1021/acs.inorgchem.6b02666},
journal = {Inorganic Chemistry},
number = 3,
volume = 56,
place = {United States},
year = {Wed Jan 11 00:00:00 EST 2017},
month = {Wed Jan 11 00:00:00 EST 2017}
}
  • Laser Raman spectra of uranyl tetrachloride complexes (K/sub 2/UO/sub 2/Cl/sub 4/, Rb/sub 2/UO/sub 2/Cl/sub 4/, Cs/sub 2/UO/sub 2/Cl/sub 4/, (NH/sub 4/)/sub 2/UO/sub 2/Cl/sub 4/) have been measured in the region from 3500 to 10 cm/sup -1/. Vibrational assignments as well as normal coordinate analyses have been carried out with the assumption that all the complexes contain discrete (UO/sub 2/Cl/sub 4/)/sup 2 -/ ions belonging to a point group D/sub 4h/. To understand the nature of the uranyl bonds in the complexes, approximate ..pi..-bonding energies of such bonds have been estimated from the U--O stretching force constants. The reliability of themore » values obtained are discussed in detail on the basis of Mulliken's magic formula.« less
  • The infrared spectra of gaseous and solid CH$sub 3$CH$sub 2$PH$sub 2$ and CH$sub 3$CH$sub 2$PD$sub 2$ have been recorded from 200 to 3500 cm$sup -1$. The Raman spectra of gaseous, liquid, and solid CH$sub 3$CH$sub 2$PH$sub 2$ and CH$sub 3$CH$sub 2$PD$sub 2$ have been recorded from 100 to 3500 cm$sup -1$. The gauche and trans isomers have been observed in the fluid phases and only the trans exists in the solid state. A vibrational assignment of the 24 normal modes has been made. Fundamental and hot band transitions have been observed for both the methyl and phosphino torsions. The methylmore » barrier in the trans d$sub 0$ molecule was determined to be 3.74plus-or-minus0.05 kcal/mole and 3.14plus-or- minus0.05 for the gauche d$sub 0$ molecule. The potential function for internal rotation around the C--P bond in CH$sub 3$CH$sub 2$PD$sub 2$ was determined and the following potential constants found: V$sub 2$=207plus-or-minus6 cm$sup -1$, V$sub 3$=785plus-or-minus5 cm$sup -1$, and V$sub 6$=-25plus-or-minus3 cm$sup -1$. The energy difference between the potential energy minima of the gauche and trans conformations is 150 cm$sup -1$, the trans being the more stable form. The calculated gauche--gauche barrier is 635 cm$sup -1$ (1.82 kcal/mole) and the trans--gauche barrier is 944 cm$sup -1$ (2.70 kcal/mole). A similar potential function was determined for the CH$sub 3$CH$sub 2$PH$sub 2$ isomer but the fit to this one-dimensional model was not as good as that for the deuterium compound probably because of greater coupling in the light molecule.« less