skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Two-dimensional hyperfine sublevel correlation spectroscopy: Powder features for S = 1/2, I = 1

Abstract

The lineshapes of two-dimensional magnetic resonance spectra of disordered or partially-ordered solids are defined by ridges of singularities in the frequency plane. The positions of these ridges are described by a branch of catastrophe theory concerning the mapping of one 2-D surface onto another. The specific case of HYSCORE spectra for paramagnetic centers having electron spin S = ? and nuclear spin I = 1 is discussed in terms of catastrophe theory using an exact solution of the nuclear spin Hamiltonian. The line shape characteristics are considered for several general cases

Authors:
;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
891114
Report Number(s):
PNWD-SA-7031
13297; TRN: US200621%%9
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Magnetic Resonance, 179(1):120-135
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; POWDERS; ELECTRON SPIN RESONANCE; NUCLEAR MAGNETIC RESONANCE; SPECTROSCOPY; CALCULATION METHODS; ESE EM; HYSCORE; 2D spectroscopy; Catastrophe theory; Nitrogen nucleus; Hyperfine interaction; Singularity patterns; Mapping; Quadrupolar interaction; Fold; Cusp.; Environmental Molecular Sciences Laboratory

Citation Formats

Maryasov, Alexander G., and Bowman, Michael K. Two-dimensional hyperfine sublevel correlation spectroscopy: Powder features for S = 1/2, I = 1. United States: N. p., 2006. Web. doi:10.1016/j.jmr.2005.11.013.
Maryasov, Alexander G., & Bowman, Michael K. Two-dimensional hyperfine sublevel correlation spectroscopy: Powder features for S = 1/2, I = 1. United States. doi:10.1016/j.jmr.2005.11.013.
Maryasov, Alexander G., and Bowman, Michael K. Wed . "Two-dimensional hyperfine sublevel correlation spectroscopy: Powder features for S = 1/2, I = 1". United States. doi:10.1016/j.jmr.2005.11.013.
@article{osti_891114,
title = {Two-dimensional hyperfine sublevel correlation spectroscopy: Powder features for S = 1/2, I = 1},
author = {Maryasov, Alexander G. and Bowman, Michael K.},
abstractNote = {The lineshapes of two-dimensional magnetic resonance spectra of disordered or partially-ordered solids are defined by ridges of singularities in the frequency plane. The positions of these ridges are described by a branch of catastrophe theory concerning the mapping of one 2-D surface onto another. The specific case of HYSCORE spectra for paramagnetic centers having electron spin S = ? and nuclear spin I = 1 is discussed in terms of catastrophe theory using an exact solution of the nuclear spin Hamiltonian. The line shape characteristics are considered for several general cases},
doi = {10.1016/j.jmr.2005.11.013},
journal = {Journal of Magnetic Resonance, 179(1):120-135},
number = ,
volume = ,
place = {United States},
year = {Wed Mar 01 00:00:00 EST 2006},
month = {Wed Mar 01 00:00:00 EST 2006}
}
  • It is shown that HYSCORE spectra of paramagnetic centers having nuclei of spin I=1 with isotropic hfi and arbitrary NQI consist of ridges having zero width. A parametric presentation of these ridges is found which shows the range of possible frequencies in the HYSCORE spectrum and aids in spectral assignments and rapid estimation of spin Hamiltonian parameters. An alternative approach for the spectral density calculation is presented that is based on spectral decomposition of the Hamiltonian. Only the eigenvalues of the Hamiltonian are needed in this approach. An atlas of HYSCORE spectra is given in the Supporting Information. This approachmore » is applied to the estimation of the spin Hamiltonian parameters of the oxovanadium-EDTA complex.« less
  • The effects of collisional resonances and radiative cascades on the linear polarization of He-like iron (Fe XXV) lines from 1[ital s]2[ital l] to 1[ital s][sup 2] levels have been investigated. Detailed calculations have been carried out for the 1[ital s]3[ital l]3[ital l][prime] resonance contributions to electron-impact excitation rates from the 1[ital s][sup 2] ground level to the individual magnetic sublevels of 1[ital s]2[ital l] configurations. Excitation collision strengths from 1[ital s][sup 2] to 1[ital s]3[ital l] sublevels as well as radiative cascade transitions from 1[ital s]3[ital l] to 1[ital s]2[ital l][prime] sublevels have also been computed. The autoionization transition-matrix elementsmore » (for the resonance effects) and the collison strengths (for the radiative cascades) have been computed in the distorted-wave approximation using intermediate coupling with fine-structure mixing multiconfiguration bound wave functions. The results indicate that the collisional resonance contributions, when averaged over a small energy range just covering them, have a somewhat significant depolarizing effect on the (1[ital s][sup 2][ital S][sub 0]--1[ital s]2[ital p] [sup 1][ital P][sub 1], electric dipole) [ital w] line, the (1[ital s][sup 2] [sup 1][ital S][sub 0]--1[ital s]2[ital p] [sup 3][ital P][sub 2], magnetic quadrupole) [ital x] line, and the (1[ital s][sup 2] [sup 1][ital S][sub 0]--1[ital s]2[ital p] [sup 3][ital P][sub 1], fine-structure electric dipole) [ital y] line. However, the averaged polarization degree over some single resonances can reach high values.« less
  • The utility of ultrahigh resolution, continuous-wave laser sources in multiphoton spectroscopy is demonstrated by measurements of fluorescence excitation spectra resulting from two-photon pumping of individual rotational branches of (3/ital s//sigma/)/ital A/ /sup 2//Sigma/+(/ital v//prime/=1,/ital N//prime/=3)/l arrow//ital X/ /sup 2//Pi/(/ital v//prime/=0) NO. The general physical significance of fine structure and hyperfine structure interactions is briefly discussed emphasizing their relation to dynamical phenomena. Current observations yield the following fine structure and hyperfine structure parameters characterizing /ital A/(/ital v/=1,/ital N/=3) NO: /gamma/=/minus/80.10/plus minus/0.04 MHz, /ital b/=40.9/plus minus/0.2 MHz, /ital c/=1.5/plus minus/4.5 MHz, and /ital eQq/=/minus/7.2/plus minus/0.5 MHz. The effective cross section for two-photonmore » excitation of /ital R//sub 11/(/ital J//double prime/=2.5) is estimated from experimental observables to be 1/times/10/sup /minus/44/ cm/sup 4/ s.« less
  • It is known that the bromination of endotricyclo(5.2.1.0/sup 2,6/)decane (I) with bromine in the presence of aluminum bromide leads to the formation of 1,3,5- and 1,3,6-tribromoadamantanes and 1,2,3,5,6,7-hexabromonaphthalene. In view of the complexity of the isomerization of the endo-decane (I) to adamantane the authors studied the bromination of (I) with bromine in order to detect the intermediate products of this isomerization. 2,4,5,8-Tetrabromotricyclo(4.2.2.0/sup 1,5/)decane was synthesized by the bromination of endo-tricyclo(5.2.1.0/sup 2,6/)decane, and its structure was determined by two-dimensional homonuclear and heteronuclear correlation NMR spectroscopy with full assignment of the signals and was confirmed by x-ray crystallographic analysis.
  • The reaction of Lu3+ or Yb3+ and H5IO6 in aqueous media at 180 C leads to the formation of Yb(IO3)3(H2O) or Lu(IO3)3(H2O), respectively, while the reaction of Yb metal with H5IO6 under similar reaction conditions gives rise to the anhydrous iodate, Yb(IO3)3. Under supercritical conditions Lu3+ reacts with HIO3 and KIO4 to yield the isostructural Lu(IO3)3. The structures have been determined by single-crystal X-ray diffraction. Crystallographic data are (MoKa, {lambda}=0.71073 {angstrom}): Yb(IO3)3, monoclinic, space group P21/n, a=8.6664(9) {angstrom}, b=5.9904(6) {angstrom}, c=14.8826(15) {angstrom}, {beta}=96.931(2){sup o}, V=766.99(13), Z=4, R(F)=4.23% for 114 parameters with 1880 reflections with I>2s(I); Lu(IO3)3, monoclinic, space group P21/n,more » a=8.6410(9), b=5.9961(6), c=14.8782(16) {angstrom}, {beta}=97.028(2){sup o}, V=765.08(14), Z=4, R(F)=2.65% for 119 parameters with 1756 reflections with I>2s(I); Yb(IO3)3(H2O), monoclinic, space group C2/c, a=27.2476(15), b=5.6296(3), c=12.0157(7) {angstrom}, {beta}=98.636(1){sup o}, V=1822.2(2), Z=8, R(F)=1.51% for 128 parameters with 2250 reflections with I>2s(I); Lu(IO3)3(H2O), monoclinic, space group C2/c, a=27.258(4), b=5.6251(7), c=12.0006(16) {angstrom}, {beta}=98.704(2){sup o}, V=1818.8(4), Z=8, R(F)=1.98% for 128 parameters with 2242 reflections with I>2s(I). The f elements in all of the compounds are found in seven-coordinate environments and bridged with monodentate, bidentate, or tridentate iodate anions. Both Lu(IO3)3(H2O) and Yb(IO3)3(H2O) display distinctively different vibrational profiles from their respective anhydrous analogs. Hence, the Raman profile can be used as a complementary diagnostic tool to discern the different structural motifs of the compounds.« less