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A FREQUENCY DEPENDENT "LEVEL CROSSING" RESONANCE IN THULIUM

NICOTINATE DIHYDRATE

Article  in  Le Journal de Physique Colloques · December 1988

DOI: 10.1051/jphyscol:19888698

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 JOURNAL DE PHYSIQUE
Colloque C8, Supplement au no 12, Tome 49, decembre 1988

A FREQUENCY DEPENDENT "LEVEL CROSSING" RESONANCE IN THULIUM

NICOTINATE DIHYDRATE

J. M. Baker (I), B. Bleaney (I), M. I. Cook (I), P. M. Martineau (I), M. R. Wells (I)
and C. A. Hutchison Jr. (2)
(I) The Clarendon Laboratory, Parks Road, Ozford 0 x 1 3PU, G.B.
(2) Chemistry Department, University of Chicago, Ill., U.S.A.
Abstract. - In TmND a strong resonance of width 170 mT occurs at a field B = 0.17 T which is found to be independent
of frequency between 2 and 600 MHz. Experiments at 15 MHz on a spherical sample of TmND at 0.5 K, to produce
narrower lines, show three equally spaced lines whose origin is explained.

Introduction

The lanthanide nicotinate dihydrates (LnND), with

the formula [ ~ ( nC S H ~ N C O(H~o),],
~)~ , for a homol-
ogous series whose monoclinic crystals, space group
P/2,,, contain two symmetry related dimers per unit
cell. Each dimer contains a pair of ~ n ions ~ ' with
separation about 0.43 nm: the two ions in a pair are
related by inversion symmetry, but at each ~ n site ~ +
there is no point symmetry.
In spite of this low symmetry, the ground state of I I I

each ~ r n ~ion,' 4f12 3 ~ , 5in

, a pair of ~ r n ~ ions
+ in 0.1
0'2 B Tesla
a dimer, is a non Kramers doublet with measured g- Fig. 1. - The lowest energy levels in TmND as a function
value close to the maximum possible theoretical value of magnetic field parallel to the K1 axis, for details see
of 12 g, corresponding to I MJ = f6 ) , [I]. The en- text.
ergy levels of the pairs of ~m~~ ions in both LnND
containing 0.01 mole fraction of Tm, and undiluted
TmND, may be described by the spin hamiltonian with
6. Hence the energy level diagram for the undiluted
S1 = S2 = 1/2,11 = I 2 = 112 :
TmND is expected to be similar to the figure, precise
details depending upon the value of 6.
In undiluted TmND a resonance line is also observed
near 170 mT at low frequencies, independent of fre-
quency between 2 and 600 MHz. The only places on
The figure shows the energy level diagram for such the figure where levels are close enough for such tran-
a spin hamiltonian with levels labelled with quantum sitions is the three crossings of levels with different MI
+
numbers MI = MII M12 and MslMsz. EPR transi- marked with heavy dots, whose separation depends
tions observed at 17 GHz in dilute material are indi- upon the value of 6, and it was supposed in [I] that
cated by vertical bars. As g, is the only non-zero com- the observed line is an unresolved superposition of the
ponent of the electronic g-matrix, only AM, = 0 tran- transitions near these level crossings.
sitions can be excited, requiring an oscillating mag-
netic field in the z direction. For 6 = 0, the eigenstates Experiments
would be pure MslMs2 between which no AMs = 0
transitions could occur. Hence the observed transi- New measurements have been made on a single crys-
tions are permitted only because of the admixture pro- tal sphere of TmND at temperature sufficiently low to
duced by the terms in 6. In undiluted TmND at 4.2 K depopulate the upper levels, in order to reduce both
no structure due to A and 6 is observed in the two macroscopic and microscopic variations in the internal
EPR lines of width 54 mT; but as the value of g, and field which contribute to the line width. The crys-
P a r e nearly the same as for the dilute material, one tal aligns itself in the applied magnetic field by rolling
expects the value of A to be nearly the same, and the until B is parallel to the K1-axis of the maximum sus-
intensities of the EPR lines suggest a similar value for ceptibility. At 1.3 K, EPR at 33 GHz in the higher

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphyscol:19888698

C8 - 1516 JOURNAL DE PHYSIQUE
field line, shows a linewidth of 15 mT, giving a good
resolution of the two line hyperfine structure: the line
separation of 30 mT gives nearly the same value of A
as for the dilute material. At 0.5 K, the resonance near
to 170 mT at 15 MHz is reduced in width to 6.7 mT
revealing three equally spaced lines with overall sepa-
ration of 30 mT.
The observation of three resolved lines appears to
confirm the level crossing model of figure 1, for which
the observed line separation corresponds to Slh =
5.3 GHz. This also confirms the deduction in [I] that
S/h for TmND should have a similar, though some-
what smaller, value than that for undiluted maerial,
6/h = 9.5 GHz.
More experimental work needs to be done to account
for the mechanism and intensities of the lines at low
frequencies. Although AMI = f1 NMR transitions
could be excited at the level crossings, the observed
lines are too strong for NMR. However, if some ad-
ditional term in the spin hamiltonian produced small
matrix elements coupling the crossing levels, electronic
AM, = 0 transitions at low frequencies would be al-
lowed near the "crossings" of similar intensity to EPR
in the GHz range. Such terms might arise through an
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enhanced nuclear Zeeman interaction or an enhanced
transferred hyperfine interaction between members of
the pair. These matrix elements would prevent the lev-
els from actually crossing, they would have a minimum
separation depending upon the magnitude of the ma-
trix element. Such a model produces large transition
probability when hv is equal to the energy separation,
A, produced by the mixing matrix element at the ex-
act "crossing point" , but the transition probability de-
creases as ( h v / ~ for
) ~higher frequencies, and should
be zero for hv < A. Unfortunately, absolute intensities
at different frequencies are difficult to compare because
of unknown frequency dependence of the sensitivity of
the apparatus. A full understanding therefore requires
very careful measurement of the frequency dependence
of intensities and a comparison with the prediction of
specific models, involving more expe~imentaland com-
putational work.
[I] Baker, J. M., Bleaney, B., Davouist, C. E., Hutchi-
son Jr., C. A., Leask, M. J. M., .Martineau, P. M.,
Robinson, M. G . , Weber, R. T. and Wells, M. R.,
Proc. R. Soc. L o n d o n A 403 (1.986) 199.