title: Nuclear Magnetic Resonance Measurements and Electronic Structure of Pu(IV) in [(Me)4N]2PuCl6.
abstract: The synthesis, electronic structure, and characterization via single-crystal X-ray diffraction, nuclear magnetic resonance (NMR) spectroscopy, and magnetic susceptibility of (Me4N)2PuCl6 are reported. NMR measurements were performed to both search for the direct (239)Pu resonance and to obtain local magnetic and electronic information at the Cl site through (35)Cl and (37)Cl spectra. No signature of (239)Pu NMR was observed. The temperature dependence of the Cl spectra was simulated by diagonalizing the Zeeman and quadrupolar Hamiltonians for (35)Cl, (37)Cl, and (14)N isotopes. Electronic structure calculations predict a magnetic Γ5 triplet ground state of Pu(IV) in the crystalline electric field of the undistorted PuCl6 octahedron. A tetragonal distortion would result in a very small splitting (∼20 cm(-1)) of the triplet ground state into a nonmagnetic singlet and a doublet state. The Cl shifts have an inflection point at T ≈ 15 K, differing from the bulk susceptibility, indicating a nonmagnetic crystal field ground state. The Cl spin-lattice relaxation time is constant to T = 15 K, below which it rapidly increases, also supporting the nonmagnetic crystal field ground state.
authors: Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
authors: Andrew M
authors: AM
authors: Mounce
authors: Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
authors: Hiroshi
authors: H
authors: Yasuoka
authors: Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.|University of California Los Angeles , Los Angeles, California 90095, United States.
authors: Georgios
authors: G
authors: Koutroulakis
authors: Department of Physics and Astronomy, Northwestern University , Evanston, Illinois 60208, United States.
authors: Jeongseop A
authors: JA
authors: Lee
authors: Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory , Richland, Washington 99352, United States.
authors: Herman
authors: H
authors: Cho
authors: Department of Chemistry, University of Buffalo, State University of New York , Buffalo, New York 14260-3000, United States.
authors: Frédéric
authors: F
authors: Gendron
authors: Department of Chemistry, University of Buffalo, State University of New York , Buffalo, New York 14260-3000, United States.
authors: Eva
authors: E
authors: Zurek
authors: Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
authors: Brian L
authors: BL
authors: Scott
authors: Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
authors: Julie A
authors: JA
authors: Trujillo
authors: Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
authors: Alice K
authors: AK
authors: Slemmons
authors: Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
authors: Justin N
authors: JN
authors: Cross
authors: Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
authors: Joe D
authors: JD
authors: Thompson
authors: Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
authors: Stosh A
authors: SA
authors: Kozimor
authors: Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
authors: Eric D
authors: ED
authors: Bauer
authors: Department of Chemistry, University of Buffalo, State University of New York , Buffalo, New York 14260-3000, United States.
authors: Jochen
authors: J
authors: Autschbach
authors: Los Alamos National Laboratory , Los Alamos, New Mexico 87544, United States.
authors: David L
authors: DL
authors: Clark