Articulo Aip

Electronic Energy Levels in the Trivalent Lanthanide Aquo Ions. I.
Pr3+,
Nd3+, Pm3+, Sm3+, Dy3+, Ho3+, Er3+, and Tm3+
W. T. Carnall, P. R. Fields, and K. Rajnak
Citation: J. Chem. Phys. 49, 4424 (1968); doi: 10.1063/1.1669893
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T'HE JOURNAL OF CHEMICAL PHYSICS
VOLUME 49, NUMBER 10
15 NOVEMBER 1968
Electronic Energy Levels in the Trivalent Lanthanide Aquo Ions.

I PrH, N d H, PmH, Sm H , DyH, HOH, Er3+, and Tm3 +*
W. T.
CARNALL,
P. R.
FIELDS, AND
K.
RAJNAKt
Chemistry Division, Argonne National Laboratory, Argonne, Ininois

(Received 2 April 1968)
The free-ion energy-level schemes of the PtJ+, Nd3+, Pm3+, Sm3+, Dya+, Hoa+, EtJ+, and Tm3+ aquo ions
have been determined from their absorption spectra in dilute acid solution at 25. Energy-level assignments
were made by comparison with crystal spectra, and on the basis of correlations between calculated and
observed band intensities. For most of the ions, it was possible to identify several transitions giving rise
to bands at energies as high as 45 000-50 000 cm-1 Sufficient numbers of assignments were made to justify
inclusion of the effects of configuration interaction in the calculation of the energy-level parameters. Variation of the electrostatic, spin-orbit coupling, and configuration-interaction parameters across the lanthanide
series is examined.
In 1907, BecquereP first showed that the absorption

bands of crystalline lanthanide compounds could be
resolved into sharp lines at low temperatures. He further reported that many of these lines exhibit a Zeeman
effect. By 1929, Bethe2 had developed the theory for
term splitting which results from the influence of a
crystalline electric field of a given symmetry on an
atom, but the gross term structure and the nature of
the sharp lanthanide absorption lines were not understood. Thus, while there was considerable interest manifest in the spectroscopic properties of the lanthanides
in the early thirties,8 the interpretation was very limited.
Experimentally, it was extremely difficult to prepare
high-purity lanthanide compounds prior to the development of the ion-exchange processes used today. Prandt14
referred to his work with the rare earths over a period
of 20 years, which finally led to the preparation of relatively pure compounds of most of the members of the
4fN series. These were used in 1934 to obtain the first
complete (except for Pm8+) set of lanthani~e-solution
absorption spectra in the range 2200-7000 A.4 Prandtl
expressed the hope that the results in solution would
stimulate further theoretical interpretation.
A comparison between theory and experiment was
given for the spectrum of Tm2(S04)38H20 in 1937,6
using the methods of Condon and Shortley.6 However
from the standpoint of computation, the complete
treatment of more complex configurations was not
practical until the development of the tensor operator
methods of Racah. 7 Thus, the investigation of the spec-
trum of Nd3+ in Nd(Br03)s9H20 by Satten in 19538

was apparently the first attempt to analyze the states
resulting from more than two equivalent f electrons
assuming Russell-Saunders coupling. Subsequent studies (for example see Refs. 9 and 10) have yielded an
intermediate coupling treatment of several of the lowlying levels in the crystal spectra of practically all the
lanthanides. The problem of extending these analyses
to higher energies is formidable because of the increase
in the density of levels to be characterized, and because
the parameters used to predict the location of terms
are normally not well enough determined to provide a
reliable guide to making assignments.
Many of the transitions characterized in crystals
containing lanthanide ions can be readily identified in
solution spectra. However, until recently there was no
independent method of establishing the SLJ assignment of a band in solution. The success of the JuddlL
Ofeltl2 theory in deducing intensity relationships in
lanthanide spectra13 ,14 suggested its application to this
problem. In the present communication we will discuss
the use of calculated intensities in extending the analysis
of lanthanide spectra both to higher energies and to
more complex systems than has heretofor been attempted.
On the basis of the numerous new assignments that
have been made, it was possible for the first time to
consider the second-order effects of configuration interaction in defining the energy-level schemes of the lanthanides.
* Work performed under the auspices of the U.S. Atomic

Energy Commission.
t Present address: Kalamazoo College, Kalamozoo, Mich.
1 J. Becquerel, Radium 4, 328 (1907); 5, 5 (1908). J. Becquerel
and H. K. Onnes, ibid. 5,227 (1908).
2 H. Bethe, Ann. Physik 3, 133 (1929).
3 S. Freed, Rev. Mod. Phys. 14, 105 (1942).
'W. Prandtl and K. Scheiner, Z. Anorg. Algero. Chem. 220,
107 (1934).
6 H A Bethe and F. H. Spedding, Phys. Rev. 12,454 (1937).
8 E: U: Condon and G. H. ShortleYl Theory of Atomic Spectra
(Cambridge University Press, Cambndge, 1957).
7 G. Racah, Phys. Rev. 62, 438 (1942).
Since the theoretical treatment of lanthanide absorption spectra has already been discussed in detail (for
8 R. A. Satten, J. Chero. Phys. 21, 637 (1953).
ENERGY-LEVEL CALCULATIONS
G. H. Dieke, Advances in Quantum Electronics, J. R. Singer,

Ed. (Columbia University Press, New York, 1961).
10 G. H. Dieke and H. M. Crosswhite, Appl. Opt. 2,675 (1963).
11 B. R. Judd, Phys. Rev. 127, 750 (1962).
12 G. S. Ofelt, J. Chem. Phys. 37,511 (1962).
13 W. T. Carnall, P. R. Fields, and B. G. Wybourne, J. Chem.
Phys. 42, 3797 (1965).
If W. T. Carnall and P. R. Fields, Advan. Chem. Ser. 71, 86
(1967) .
4424
ENERGY LEVELS OF TRIVALENT LANTHANIDE AQUO IONS. I
example see Refs. 15 and 16), only the general outline

of the calculations need be included here.
The observed spectra of the trivalent lanthanides in
solution or in crystal lattices arise from "forbidden"
transitions within the ground 4jN configuration. I6 To a
first approximation, the energy-level structure of the
4fN configuration arises from electrostatic and magnetic
interactions between the 41 electrons. These interactions
may be represented by the Hamiltonian
X=X.+X.o,
(1)
where X. involves the Coulomb interaction between
pairs of 1 electrons and Xso takes into account the coupling of spin and orbital angular momenta which is the
most important magnetic interaction for 1 electrons.
Expansion of the electrostatic interactions in terms
of Legendre polynomials allows separation of variables
and leads to the result
6
E.= 2:.PFk
(k even).
(2)
k=O
In Eq. (2), the electrostatic energy (Ee) is expressed

in terms of products of Slater radial integrals, F k , and
angular coefficients, p. Similarly, the energy arising
from spin-orbit interaction (E.o) may be written
.
(3)
in which A.o represents the angular part of the spinorbit interaction and t4{ is a radial integral. The total
energy in this approximation is, then, E.+ Eso.
The angular terms are evaluated using Racah's tensor operator formalism,1 and an intermediate coupling
scheme with Russell-Saunders (SIJ) basis states. In
practice the radial integrals are treated as parameters
to be determined from the experimental data. Neglecting the effect of fOFo, which is only a scaling factor,
there remain three parameters associated with electrostatic interactions, F2, F4, F 6 , and one parameter, t4{'
associated with spin-orbit interactions. There exist in
the literature very few cases where all four parameters
were derived by a least-squares fit to energy levels for
which J assignments have been made. Further approximations are usually necessary, since to adequately
determine all the parameters simultaneously requires
assignments to levels within a number of different
multiplets. In many instances only levels in the ground
multiplet and the first two or three excited multiplets
have been clearly identified. One frequently used approximation assumes that the 41-radial wavefunction
is hydrogenic. This makes it possible to calculate ratios
of the Slater integrals16 ;
F 4/F 2 =O.138,
(4)
F 6 /F 2 =O.0151.
(5)
16 J. P. Elliott, B. R. Judd, and W. A. Runciman, Proc. Roy.

Soc. (London) A240, 509 (1957).
16 B. G. Wyboume, Spectroscopic Properties of Rare Earths
(John Wiley & Sons, New York, 1965).
4425
As Wybourne16 has pointed out, this approximation

happens to yield ratios of Slater integrals that are useful in the calculations and does not imply anything
about the actual shape of the eigenfunctions. It should
be noted that the splitting of the ground multiplet is
rather insensitive to the values of Fk Initial estimates
of Fk and t4! for all of the lanthanides have been tabulated. l4 16
When the methods of Racah7 are used to calculate
the matrix elements of electrostatic interaction, operators are constructed such that they have simple transformation properties with respect to the symmetry
groups used to classify the states. In this system the
electrostatic energy becomes
(6)
where the ek's are the angular parts of the new operators and the Ek's are linear combinations of the Fk'S.I5
It has been shown I7- 20 that the effects of configuration interaction must frequently be considered in order
to obtain an adequate interpretation of the energy-level
schemes of lanthanide ions. This can be accomplished
in second-order perturbation theory by adding to the
Hamiltonian certain model interactions acting wholly
within thefN configuration. 21 Such a procedure accounts
for that part of the interaction which does not have
the same angular form as the coefficients, ek, of the
electrostatic-interaction parameters. The part that does
have the same form as ek is automatically absorbed in
the Ek parameters.
ForjN configurations, the additional interactions may
be written as
X' =aL(L+ 1) +/1G(G.!) +yG(R7 )

+three-particle terms,
(7)
where a, /1, and 'Yare linear combinations of radial

integrals and are treated as adjustable parameters.
G(G2 ) and G(R 7 ) are eigenvalues of Casimir's operator for the groups G2 and R 7 , respectively, and have
been tabulated by Wybourne. 16 The effects of the threeparticle terms are smaller than those of a, /1, and 'Y,
and the accuracy of the present data does not warrant
their consideration here. I8 For some ions, the parameters a and /1 have been determined previously (the 'Y
used by Trees22 is 1/12 of the /1 used here) but crystal
studies frequently do not allow assignment of a sufficient number of levels for a least-squares fit of six
parameters (E1, E2, 3, tv, a, and j3). 'YG(R7) is re17 K. Rajnak and B. G. Wybourne, J. Chem. Phys. 41, 565
(1964) .
18 K. Rajnak, J. Chem. Phys. 43, 847 (1965).
111 J. Sugar. Phys. Rev. 14, 731 (1965); H. M. Crosswhite
G. H. Dieke, and W. J. Carter, ]. Chem. Phys. 43, 2047 (1965):
20 K. Ra~nak and W. F, Krupke, J. Chem. Phys. 46, 3532 (1967).
21 K. RaJnak and B. G. Wyboume, Phys. Rev, 132, 280 (1963).
22 R. E. Trees, J. Opt. Soc. Am, 54, 651 (1964).
4426
CARNALL, FIELDS, AND RAJNAK
lated to the correction (3Q used by Racah23 and Trees. 22

'Y is expected to be important only in cases where large
components in the eigenvectors of the observed levels
have a seniority number different from that of the
ground state. An attempt to determine 'Y has previously been possible only for the free-ion spectrum of
PrH.24
It should be noted that 'Y and El are not independent; they are related by a common term S(S+1) in
their coefficients. Thus, changes in El are expected
when 'Y is added to the calculation.
ENERGY-LEVEL FITTING PROCEDURE
In the trivalent lanthanides, the free ion is only
slightly perturbed by the electric field of the crystal
or solution matrix in which it is observed. Each freeion level, characterized by the total angular momentum
quantum number, J, is split by this electric field into
a manifold of not more than 2J 1 components. The
splitting does not usually encompass more than ,...,200300 em-I.
In crystal spectra, Zeeman and polarization studies
have made it possible to characterize the J manifolds
to which many of the lower-lying crystal levels belong.
At higher energies this becomes more difficult. There
is an overlapping of components of many different J
levels, and unambiguous assignments are not possible.
In solution spectra the crystal-field components are
usually not resolved, so the observed absorption bands
can only be characterized in terms of the free-ion levels
involved. At lower energies the different J manifolds
are frequently isolated and the energy of the transition
may be assigned to the center of the observed band.
The assignments at this point are based on comparison with crystal spectra. These led to an initial estimate
of the values of the parameters Fk and S4! for all of the
lanthanide aquo ions. 14 However, the limited usefulness
of these first parameters should be emphasized. In the
lanthanides, the lower levels are usually rather pure
L-S states, whose composition does not change appreciably with small changes in Fk and S4!. It might be
anticipated that estimates of these parameters based
only on relatively pure low-lying levels would yield
poor predictions for the energies of higher states which
are not as pure.
Based upon approximate Fk and S4f parameters we
showed13 14 that the Judd-Ofelt theory was able to correlate the intensities of the solution absorption bands
observed in the near-infrared and a limited portion of
the visible region of the spectrum, for all of the lanthanides from Pr3-I- to Yb3+. We noted that the values
of the calculated matrix elements of U(lI), as discussed
in the accompanying paper/Ii were rather insensitive
G. Racah, Phys. Rev. 85, 381 (1952).

K. Rajnak, J. Opt. Soc. Am. 55, 126 (1965).
W. T. Carnall, P. R. Fields, and K. Rajnak, J. Chern. Phys.
49,4412 (1968).
23
24
26
to small variations in Fk and t4j. Thus, it appeared

reasonable to assume that changes in these parameters which were occasioned by progressively improving the energy-level fit would produce only minor
variations in the magnitude of the matrix elements
of U(lI). A single set of three parameters, :lA, is required
by Judd's theory to obtain all the calculated intensities
for a given lanthanide ion in a given medium. 13 The
intensity of a particular transition is proportional to
:lAu(1/;J II V().) 111/;'1')2. Thus, large matrix elements
of U(A) for a transition imply a large calculated intensity.
It was found that throughout the visible and ultraviolet regions of the spectrum (to 50000 em-I), there
were numerous instances where single transitions with
large matrix elements of U(4) and/or U(6) occurred near
the same energy as a number of transitions with very
small matrix elements of U(A). In many cases it was
clear that the theory could account for the experimental data only if the transition with large matrix elements were assigned to a relatively intense absorption
band. Thus, the intensity calculations, based upon approximate values of Fk and S4f> were used to make
additional assignments to the observed spectrum. Intensity relationships then became a tool for improving
the energy-level parameters.
The fitting procedure adopted here consisted of first
making energy-level assignments to the centers of those
absorption bands, which were clearly characterized by
comparison with data obtained in the analysis of crystal spectra. The parameters Ek and f4! were determined
by a least-squares process. 13 The resulting eigenvectors
were then characteristic of the levels observed in solution. These eigenvectors were used to calculate the
matrix elements of U().) for all transitions to 50000
em-I. Several additional assignments were obvious at
this point for each lanthanide considered. The fitting
process employing all assigned levels was then repeated
to determine new values of Ek and f4!.
In most cases, new assignments were made at only
slightly higher energies than those involved in previous
assignments, and the calculations were repeated a number of times. Thus, there were no abrupt changes in
Ek and f4!. Actually, as would be predicted, the value
of S4! was relatively well defined early in the fitting
procedure.
For Pr3+, Nd3+, Pm3+, Ho3+, Er3+, and Tm3+, the
number of assignments which could be readily made
was sufficient to justify inclusion in the fit of the
configuration-interaction parameters, a and {3, as soon
as the first two or three calculations were completed.
Some higher energy levels were assigned subsequently
such that 'Y could be defined. In the spectra of Sm3+
and Dy3+, some of the bands in the visible range were
found to be strongly dependent upon 'Y. Failure to
recognize this fact, by including assignments for these
levels in a six-parameter fit, led to poor agreement
between observed and calculated energies over the
L:A
ENE R G Y LEV E L S 0 F T R I V ALE N T
whole spectrum. Exclusion of these strongly /'-dependent levels in a six-parameter fit resulted in a good fit
for all other levels, but a difference of as much as
300-400 cm-I between calculated and observed energies of /'-dependent levels.
ln1iuence of Stark Components in the Ground
State on Bandwidth
At room temperature, it can usually be assumed
that a small percentage of the transitions may arise
even from the highest Stark component of the ground
level. One would, therefore, predict that a band observed at room temperature would be appreciably
broadened by the presence of additional components
on the low-energy side compared to the band observed
at low temperatures. Thus, by assigning to the transition in question an energy corresponding to the center
of such a broadened band, an error, always in the
?irection of too Iowan energy, would result. Actually,
It can be demonstrated that the indicated effect is
small.
Since the energies of the crystal-field components of
many of the levels for Nds+ in LaCIa 26 and in LaFs 27
have already been recorded at low temperature, we
examined the spectra of similar crystals at room temperature. The spectra were recorded with the same
instrument that was used in the other work reported
here. 26 Assignments of energies were made on the same
basis as was used for the solution spectra. The results
obtained are given in Table I. It was found that in
general the satellites to a band arising from transitions
which originate in one of the higher Stark components
of the ground level are relatively weak and do not
appreciably affect the center of the band observed at
room temperature as compared to that established at
liquid-He temperature. In some cases, the satellites
are well resolved from the principal band and can be
clearly identified. For example, the incompletely resolved group of bands centered at 11 441 cm-I for Nd3+
in LaCIa could be assigned to transitions arising from
the lowest Stark component in the ground level and
terminating in 4FS/2 level. Two isolated satellites, one
centered at 11 322 cm-I and a second weaker band at
11198 em-I, were assigned to transitions from known
Stark components of the ground Ievel26 at 115 and
244 em-I, respectively. We conclude that except in
cases of resolved satellites, the process of assigning
energies based on centers of bands observed at room
t~mperature does not appear to be subject to any sigmficant error.
DATA ANALYSIS AND RESULTS
In this section we will discuss some of the individual

assignments made to the lanthanides considered. In
26 E. H. Carlson and G. H. Dieke, J. Chern. Phys. 34, 1602
(1?r61); F. Varsanyi and G. H. Dieke, ibid. 33, 1616 (1960).
H. H. Caspers, H. E. Rast, and R. A. Buchanan, J. Chern.
Phys. 42, 3214 (1965).
LAN T HAN IDE A QUO ION S. I
4427
TABLE~. Comparison .between the centers of gravity of levels

for Nd3+ m LaC]' and m LaF. crystals observed at liquid-He
temperature and at room temperature.
S'L'J'
41111.
'116/'
'F'/2
'Fi/i
'H 9!1
'Fm
'SIll
'Fm
'Huts
'Gi/2
Nd3+ in LaC],
Nd3+in LaFa
,,(ern-1)
(liquid He)a ,,(ern-1) b
,,(ern-1)
(liquid He) 0 ,,(ern-1) b
4010
11 439
12 466
12
13
13
14
15
17
618
437}
524
722
935
135
3 937
4089
4000
11 613
12 610}
12 707
11600
13 386
13646
13 586
14577
15 847
17094
14 849
16 050
17 328d }
14 792
16025
11 441
12 422
17 551 d
!GT/I
'KlIII
'GT/.
'Glli
IKl 6/,
IGB/.
(tD,IF).!1
'Gtus
sPl/1
IDi/1
19 020
19434
21
21
21
23
23
056
129}
426
214
780
18
19
20
21
939
379
876
141
12 610
17 391
19 239
19 700 b
19 230
19 607
23468
23474
21 459
23239
23 781
a Reference 26.
b Present measurement for center of band observed at room temperature.
o Reference 27.
d Approximate center of gravity calculated from incomplete data.
each case, the literature was searched for the results

of investigations in crystal media, and a single comparison standard for the solution spectrum was chosen.
The most common crystal host employed by other
investigators f~r such studies has been LaCIa. It happens
that the free-IOn energy levels of the lanthanides in
this medium generally correspond quite closely to the
centers of bands observed in solution.
The energy of the ground state in solution was
equated to the average energy of the ground-state
Stark components obtained from crystal spectra. Similarly, where transitions to higher levels of the groundterm multiplet have been observed in a reference crystal but not in solution, the assumption was made that
they would be observed in solution at essentially the
same energy.
The experimental conditions and techniques of our
own work, which comprises all of the solution results
reported here, were identical to those described in Refs.
13, 14, and 25. Thus, the deuterated and normal aqueous solutions employed made possible measurements
in the range ",6000-50000 em-I. References are cited
for a few additional bands in the range ",4000-6000
cm-1 which we have observed for lanthanide nitrates
dissolved in molten LiN03-KNOs eutectic. 21HO We have
28 W. T. Carnall, D. M. Gruen, and R. L. McBeth J. Phys.
Chern. 66, 2159 (1962).
'
: w. T. Carnail, J. Phys. Chern. 67, 1206 (1963).
W. T. Carnall, P. R. Fields, and G. E. Toogood J. Phys.
Chern. 68, 2351 (1964).
'
~
N
00
TABLE II. Energy-level parameter values calculated for the trivalent lanthanides in various media (in cm-1).
(3
'Y
No of
levels fit
23.6841.2
22.899O.87
-585.4172
-676.9746
727. 7845
599.5142
13
13
18.642O.88
21.2551.2
-754.2055
-799.9472
1396.260
1342.962
13
13
(J
22
:;d
1321.384
32
;..-
789. 74370
22
r
r
Matrix
E1
E2
E3
t4/
r=ion.
4864.65.5
4713.85.0
23. 138O .15

21.890O.1O
488 . l1O. 97
464. 23O. 73
758.826.9
742. 684,4
4548.17.2
4548.27.5
21. 659O.16
21. 937O.15
470.02O.88
466. 73O.96
743.246.0
740. 758. 7
4974.613
23. 734O.22
478.031.1
879.425.7
-0.81741.2
-163.9453
aq
4739.316
23.999O.16
485.961.0
884.586.3
O.56111.4
-117. 1556
Pm8+ aq
4921.662
24.522O.74
525.531.6
1000.87.4
10.9912.5
-244.8870
5594.928
27.3650.57
545.503.4
1162.515
16.1922.8
-54O.36176
5496.942
25.8090.14
556. 4O 1. 7
1157.35.8
22.2501.3
-742.5553
6411.219
28.5440.25
603.842.0
1923,48.0
38.6612.3
-1184.789
6119.658
3O.O120.20
610. 142.2
1932.07.8
37.062l.9
-1139.174
6520.2104
31.4380.52
620.762.1
2138.39.2
23.4901.6
aq
6440.635
30.2200.18
624.39O.95
2141.34.9
LaFa l
6855.317
6884.425
32 . 126O .22
32.586O.21
645.572.4
649.642.0
LaClai
aq
6885.322
6769.9130
32. 2720. 24
32.3880.14
7150.892
7142.460
LaClsb
Pr3+
LaFsa
aq
t
t
t
t
r=w.
aclsd
NdH
aclso
SmH
aq
aClaf
DyH
aq
aClall
;..-
20
48
...."'i
16
2395.3300
34
t::1
en
-803.3063
887.56516
23
23.635O.88
-807.2036
1278.4190
41
2369,411
2380.09.7
20.3852.6
17.0442.4
-666.60107
-527.0383
27
21
:;d
64l.142.6
646.621.2
2379.511
2380.78.3
17.4312.2
18.347l.2
-655. 2886
-509. 2858
20
27
33. 886O. 62
675.735.2
2628.128
14.6886.4
-74l.59333
12
33. 7950.41
674.273.4
2628.718
14.6774.2
-631. 79216
12
796. 64216
HOH
trJ
;..t::1
;..-
Er3+
{EthYl sulfate
Tm8+
aq
Reference 19.
b Reference 32.
Reference 33.
d Reference 26.
Reference 35.
tH. M. Cl'OISWhite and G. H. Dieke.
iIM. 37, 2364 (1962).
Reference 20; G. H. Dieke and B. Pandy.

b Reference 36.
I Reference 37.
i Reference. 17 and 38.
k References 39--42.
II
&
649. 71640
J. Chern. Phy 41, 1952 (1964).
J. Chern. Phys. 35,1535 (1961); J. D. A1ce and G. H. Dieke,
......
Z
;..-
I"'l
ENERGY LEVELS OF TRIVALENT LANTHANIDE AQUO ION S. I
4429
TABLE III. Energy-level assignments for Pt'+.

Pt'+ in LaClab
Pt'+ Free ion a
S'L']'
3H.
3H,
3H,
8F,
BF.
IF.
IG.
IDs
aP D
aPI
11&
E.xptl
Eeal.d
AE
E..ptl
(em-I)
(em-I)
(em-I)
(em-I)
0
2 152.2
4389.1
4996.7
6 415.4
6 854.9
9 921.4
17 334.5
21 390.1
22007.6
22 211.6
23 160.9
50090.3
20
2 147
4 375
4 989
6406
6888
9903
17 329
21 362
21 984
22 211
23 214
50 090
-20
5
14
8
9
-33
18
99.3
2209
4390
4 906
6 322
6766
9 766
16 714
20 475
21 081
21 410
22 227
48800
ap,
ISo
rms Deviation
28
24
1
-53
0
36
Eexp\l
(em-I)
(em-I)
118 .
2200
4380
4911
6 305
6790
9 753
16709
20 450
21 057
21 410
22 279
48 800
a Reference 19.
b Reference 32.
Reference 33.
Pt'+in LaF.
AE
Ecalod
E I.d
(em-I)
200
2363
4464
5 215
6 555
7 031
9 997
16 846
20 925
(21 473)
21 519
22 754
46 900
-9
9
10
-5
17
-24
13
5
25
24
0
-52
0
33
AE
(em-I)
(em-I)
228
2 309
4490
5 182
6 581
7044
9 989
16 850
20 899
21 528
21 519
22 722
46900
-28
54
-26
33
-26
-13
8
-4
26
-55
0
32
0
47
d The parameters used to generate this set of energies are given in

Table II.
Based on the lowest three Stark levels in the 'P,-II6 manifold.
found that where comparison is possible lanthanide

absorption bands in the latter medium occur at essentially the same energies and with nearly the same
intensities as those observed in aqueous solution. The
only exception involves those bands which show a
hypersensitivity to medium effects. 13 31 We have already pointed out that there is a one-to-one correspondence between the hypersensitivity of a lanthanide
absorption band, and very large calculated values of
the matrix element of U(2) for the transition giving
rise to the band. 13 14 Such a correlation provides additional criteria for making assignments.
The intensity calculation has been discussed elsewhere. 13 26 The tables included here"contain the matrix elements of U().) , since thesetmatrix elements
form the basis for making most of thelassignments.
We adopted the following convention for U('A) =
(l/IJ II U().) II l/I'J') 2: where (l/IJ II U().) IIl/I'J') <10-7 ,
U(A) =0; where 0.00005< U(A) > IX 10-14, U(A)~O.
The parameters, Ek, !;4J, 01, (3, and /" are summarized
TABLE IV. Energy-level assignments and matrix elements of U().) for Pr8+ (aq).
S'L']'
3H.
3H6
aHs
aF2
3Fa
'F.
IG.
IDs
ap.
3PI
lIs
ap,
ISO
E ptl
E....lo
AE
(em-I)
(em-I)
(em-I)
U(2)b
U(4)b
U(6)b
200
2 3604 500d
5 200d
6500
6 950
9 900
16840
20750
21 300
21 500
22 520
46 900
245
2 322
4 496
5 149
6540
6 973
9 885
16840
20706
21 330
21500
22 535
46 900
-45
38
4
51
-40
-23
15
0
44
-30
0
-15
0
48
0.1095
0.0001
0.5089
0.0654
0.0187
0.0012
0.0026
0
0
0.0093
",0
0
0.2017
0.0330
0.4032
0.3469
0.0500
0.0072
0.0170
0.1728
0.1707
0.0517
0.0362
0.0070
0.6109
0.1395
0.1177
0.6983
0.4849
0.0266
0.0520
0
0
0.0239
0.1355
0
rms Deviation
The parameters used to generate t "i. set of energies are given In

Table II.
bU(h)
-(,yJ II U().) ",y'J')I.
Assumed energy based on data in Ref.
33.
d Based on data in Ref. 28.
C. K. JfIlrgensen and B. R. Judd, Mol. Phys. 8,281 (1964); B. R. Judd, J. Chern. Ph:ts. 44,839 (1966)
4430
CARNALL,
TABLE
FIELDS, AND RAJN AK
V. Energy-level assignments and matrix elements of U(X) for NdH (aq).
N dH in LaClaa
Euptl
S'L']'
411311
'11512
4Fm
'Fb12
2H9/2
'F112
'Sm
'F912
2H11I2
'G. '2
(em-I)
(em-I)
146
028
010
058
438
466
618
437
524
722
935
135
178
2043
4 029
6092
11 475
12 517
12 710
13 504
13 435
14 793
16001
16 999
17 194
18 874
18 965
19 369
20 858
21060
21 191
21 357
23 050
23 750
26 158
27 990
28 187
28 388
28 563
2
4
6
11
12
12
13
13
14
15
17
2G1/2
IKta/2
'G7/t
'G9IJ
2KlS/2
2G912
(2D,2P)3/2
'GUll
2Pl/I
2D5/1
(IP,2D)3/2
'Dm
19 020
19 434
21 056
21 129
21 426
23 214
23 780
26160
27 981
'D.,2
2IU/2
'D1I2
I1E
(em-I)
41911
4Iu/'I.
Eoa1.b
NdH (aq)
28 505
E ptl
(em-I)
-32
-15
-19
-34
-37
-51
-92
-67
89
-71
-66
136
146 d
2 028 d
40500
6 050
11 460
12 480
12 590
13 500
13 500
14 700
15 870
17 300
17 460
16
21
45
-30
-67
-93
-148
40
-65
-154
-156
133
127
55
19 160
19 550
21 000
21 300
21 300
21 650
23 250
23900
26300
28300
28500
130
2007
4005
6 080
11 527
12 573
12 738
13 460
13 565
14 854
16 026
17 167
17 333
19 018
19 103
19 544
21 016
21 171
21 266
21 563
23 140
23 865
26 260
28 312
28477
28 624
28 894
29260
29 966
30 554
30 747
32 567
33 481
33 913
34 474
38504
39 926
47 696
48 586
64
-4
-62
69
164
30
2
-9
-58
28 850
2111/2
30500
'Dl/1
ILll/!
2H9/t
33400
IDa/l
tHu/'/.
JDm
34 450
38500
39 950
47 700
48 600
IF./2
2F1I2
2G912
2Gl/2
84
rms Deviation
a Reference 26.
b The parameters used to generate this set of energies are given in
Table II.
in Table II for all the systems examined. The values

given are all based upon fitting procedures carried out
during the present investigation.
PrH (p)
There are numerous references to the energy-level
structure of PrH, but for purposes of comparison with
the data obtained in solution, the free-ion levels19 and
those reported for p r3-t in LaCla 32 and in LaF3 33 are
12 R. Sarup and M. H. Crozier, J. Chern. Phys. 42,371 (1965);
J. Markovsky, W. Low, and S. Yatsiv, Phys. Letters 2, 186
(1962) .
NIH.
H. Caspers, H. E. Rast, and R. A. Buchanan, J. Chem.
Phys.43, 2124 (1965).
I1E
(em-I)
2LI.,2
rms Deviation
E.a1.b
(em-I)
57
6
-16
129
34
87
110
35
40
-12
23
-44
-54
-81
-24
-4
24
4
14
88
U(2)c
0.0194
0.0001
0
0
0.0010
0.0092
0
0.0010
0.0009
0.0001
0.8979
0.0757
0.0068
0.0550
0.0046
0
0.0010
0
",0
0
",0
0
0
0.0001
0.0049
0
0
0.0001
",0
0
0.0001
0
0.0001
0.0007
0.0021
",0
",0
0.0004
U(4)c
U(6)c
0.1073
0.0136
0.0001
0.2293
0.2371
0.0080
0.0027
0.0422
0.0092
0.0027
0.4093
0.1848
0.0002
0.1570
0.0608
0.0052
0.0148
0.0188
0.0053
0.0367
0.0002
0.0014
0.1960
0.0567
0.0146
0.2584
0.0248
0.0013
0.0037
0.0010
0.0085
0.0112
0.0001
0.0006
0.0033
0.0004
0.0015
0.0024
1.1652
0.4557
0.0452
0.0549
0.3970
0.1154
0.2352
0.4245
0.0417
0.0104
0.0359
0.0314
0.0312
0.0553
0.0406
0.0143
0.0139
0.0002
0.0080
0
0.0021
0.0008
0.0170
0.0275
0.0034
0
0.0097
0.0017
0.0080
0.0012
",0
0.0012
0.0002
0.0034
",0
0.0007
0.0001
0.0002
U (1\) = (1/11 II u(X) 11.p'J') t.

d Assumed energy based on data in Ref. 26.
e Based on data in Ref. 28.
particularly relevant. The assignments, together with

the levels calculated based upon seven-parameter fits
to the crystal and free-ion data, carried out during the
present investigation, are shown in Table III. The
experimental results in solution are given in Table IV.
It was concluded that in this case the energies assigned
to solution bands corresponded most closely with those
obtained for PrH in LaF3
Most of the assignments shown in Table IV were
to resolved absorption bands. Curv~ fitting25 to the 3p
group resolved a band centered at 21500 cm- I which
was attributed to lIe. Since in this case it was necessary
to assign an energy to the ISO transition in order to
determine the value of the configuration-interaction

parameter "I, it was assumed that the energy of the
transition in solution corresponded to that assigned in
LaFa. In solution, a relatively intense absorption bandl4
is observed at >43500 cm- I due to transitions 4JN---'lo
4JN-I 5d. Calculation indicates that the ISO band should
be weak, and indeed no transition is observed superimposed on the intense j---'lod absorption.
The parameters of a six-parameter fit excluding the
assignment to ISO, except for E, are identical to those
which include "I and the ISO energy.
Nd 3+ (P)
A comparison of the energies for Nd3+ transitions in

LaCIa 26 and LaFa 27 with the centers of band systems
in aqueous solution revealed a close correlation with
the data for N d3+ in LaCIa (Table V).
The 4(;5/2 transition is hypersensitive l3 ,31 and thus
was clearly identified with a band at 17 500 cm-t,
whereas a resolved component at 17460 cm-1 was assigned to the weaker 2G7 / 2 level. Of the transitions to
2K13/2 and 4G 7/ 2 which calculated near to the same energy, the latter was assigned to the center of a band
at 19 160 cm-I since the former could not account for
the observed intensity.
Isolated bands are observed in Nd3+ even at high
energies. The intensity calculation based on parameters
fit to the assignments made at <35000 cm-I predicted
only four relatively weak transitions in the 3500050000 cm-I range. Since the eigenvectors of 2F6/2 and
2F7/2 revealed that both states involve large percentages of components differing in seniority number from
that of the ground state, it was possible to determine
the parameter "I after assigning energies for these two
levels.
A center for the Stark components of the ground

term 514 was assumed to be ,.......150 cm-I . No spectroscopic investigations of Pm3+ in a crystal lattice have
been reported. The energies of the 517 and 518 levels
are unknown, but the other levels in the ground-term
multiplet have been observed (Table VI).
Preliminary intensity calculations showed that it was
reasonable to assign the five transitions 5F1 ,2,3,4, 5S2 to
the centers of resolved bands in the 12 000-15 000 cm- I
range, and to place both sF5 and 3K1 at 15 900 cm- I ,
where the absorption was well isolated. Both the transitions to 5G2 and 5G3 were identified with known hypersensitive bands at 17700 and 18300 cm-I 30
Gruber and Conway34 reported finding three relatively intense, well-resolved bands near 30000 cm- I .
Using the assignments at <30000 cm-I as the basis,
a preliminary calculation showed that among the numerous transitions predicted to occur near 30 000 cm-t,
M J. B. Gruber and J. G. Conway,
303 (1960).
J.
Inorg. Nuc!. Chern. 14,
4431
only three had large matrix elements of U(A): 5Do, 5DI ,

and 5D2 The observed relative intensities of the bands
were in keeping with the predicted intensity pattern.
The energies of the 6FI / 2 and 6Fs/2 levels in Sm3+ were

assigned after comparing results in aqueous solution
with those in a fused nitrate salt. 28 Preliminary calculations showed that the intensity of the 6F3/ 2 transition
was in good agreement with that of the band observed
in aqueous solution at 6630 cm-I . Since a large matrix
element of U(2) was calculated for the 6FI / 2 level (Table
VII), the corresponding absorption band was identified with a hypersensitive transition. In aqueous solution only a tailing to the infrared of the band associated
with the 6Fs/2 level could be observed, but in the nitrate
melt an intense absorption was found centered at 6400
cm-I The latter energy was, therefore, also assigned
to the transition to the 6F1/ 2 level in aqueous solution.
Although a very large number of transitions occur in
the range 29 000-50 000 cm-I, only a very few had
calculated matrix elements of U(A) that could account
for the magnitude of the observed absorption bands.
The levels whose eigenvectors contain appreciable
components of states with seniority number different
than that of the ground state are usually found at
higher energies. However, in Sm3+ the eigenvectors of
the 4G6/ 2 and 4Fs/2 levels, which are identified with isolated absorption bands near 18000 cm-t, contain appreciable contributions from states of seniority number 3.
Thus, to obtain a good fit to these two levels where
the assignments are unequivocal, the parameter "I
should be included. Unfortunately, there have been
relatively few assignments made to the spectrum of
Sm3+ in LaCIa.a5 Most of the assigned levels above
17000 cm-I (Table VII) are expected to be dependent
on "I, so it is not possible to obtain a six-parameter
fit while excluding assignments dependent on "I. The
parameters given for Sm3+ in LaCIa (Table II) must
therefore be considered only approximate. A sufficient
number of assignments were made to determine all
seven parameters from the solution data.
The assignments for Dy3+(aq) were derived primarily from intensity correlations since investigations in
crystals have been very limited. A known hypersensitive
band29 at 7700 cm- I confirmed the assignment of the
transition to the 6Fu /2 level at this energy (Table VIII).
Recently, we attempted to define approximate electrostatic and spin-orbit parameters for Dy3+(aq) by assignments to several well-defined, lower-energy absorption bands. 14 A poor correspondence was found between
calculated levels and those observed levels which were
36 M. S. Magno and G. H. Dieke,
(1962) .
J.
Chern. Phys. 37, 2354
4432
CARNALL, FIELDS, AND RAJN AK

TABLE
VI. Energy-level assignments and matrix elements of U(X) for Pm3+ (aq).
E v']
(em-1)
S'L'J'
51,
515
516
517
5Is
1504
6
12
12
13
14
14
15
15
oF1
oFs
sFs
5S,
5F,
5F.
aKa
8K7
8H,
5c,
85()d
600d
400
820
600
300
650
900
900
17 300
17 700
18300
DCa
3K a
3H.
DG,
3Ga
20 250
5G.
3D2
21 900
5Ge
22300
22300
3L7
3D1
3L8
3G.
8H e
3L9
(3M,1Lh
3Da
3P,
(1D,SPh
23500
24800
BGo
IF,
sPI
3Mg
8Ft
3Is
3F,
3M1o
3Fa
3le
1L8
8f?
5Do
5D1
30040
30 480
sFa
5D2
31 250
Eoaloa
(em-1)
99
1 577
3 186
4 876
6611
12 398
12 811
13 651
14 337
14 562
15 863
15 875
17 163
17 327
17 857
18 256
18 719
19 617
20 181
21 102
21 998
22 178
22 262
22 372
23 321
23444
23 897
23995
24 412
24 462
24800
25066
25 538
26 235
26643
27 051
27 804
27 894
27916
28 193
28 395
28 810
29 078
29 189
29 587
29 979
30 471
30 816
31 266
llE
(em-1)
U(4)b
U(6)b
51
-26
-11
2
9
-51
-37
88
37
25
-27
-157
44
rms Deviation
The parameters used to generate this set of energy levels are given in
Table II.
b U (h) = <1/IJ U(~) 1/1' JI)
II
U(2)b
II
included in the fit. As we extended the earlier study

by including the parameters IX and fJ, the fit to observed
energies remained poor. Although calculated matrix
elements of U<X) clearly indicated that certain transitions should be observed within rather narrowly defined
69
-98
38
-72
56
0.0246
0.0018
0
0
0
0.0026
",0
~
0.0005
",0
0.0024
0
0.0064
0.7215
0.1444
0
0.0001
0.0093
0.0228
0.0003
0.0072
~
0
0
0
0.0013
~
0
0
0.0007
0
~
61
9
-16
78
0.0002
",0
0
0
0.0091
0.0042
0.0048
0
0.0002
0.0003
0
0
0
0
0.0012
0
0.1172
0.0301
0.0025
~
0.1404
0.1992
0.1041
0.0011
0.0291
0.0021
0.0025
0.0020
0.0210
0.2433
0.2655
0.0003
0.0057
0.0957
0.0652
0.0103
0.0025
0.0002
0.0016
0.0001
0.0019
0.0112
0.0002
0
0.0045
0.0032
~
0.0002
0.0006
0.0005
0.0003
0
0.0062
0.0004
0.0097
0
0.0031
0.0006
0.0015
0.0001
0.1520
0.2361
0.0096
0.1013
0.9694
0.6893
0.1581
0.0103
0
0.1264
0.4253
0.2295
0.2403
0.0346
0.0104
0.0200
0.0240
0.0041
0.0454
0.0088
0.0062
0.0787
0.0075
0.0365
0.0028
0.0008
0.0099
0
0.0133
0.0044
0.0041
0.0019
0.0013
0.0095
0
0.0003
0.0007
0.0008
0
0.0007
",0
0.0006
0.0025
",0
0.0013
0.0011
0.0008
0.0002
0
0
0.0046
0.0214
Assumed center of Stark components of the ground level.

d Based on data in Ref. 30.
energies, the error was 200-300 cm-1 in a number of

cases. We could not make any satisfactory progress in
the fitting procedure until we recognized the crucial
importance of 'Y in the fitting process. At the outset,
because of the paucity of assignments, the use of a
ENERGY LEVELS
TABLE
OF
VII. Energy-level assignments and matrix elements of U().) for SmH (aq).
SmH (aq)
SmH in LaClaa
Eexpd
Eoalob
S'L'J'
(em-I)
(em-I)
6H5/1
6H7I2
6H 9/J
6HU/2
36
1 080
2 286
3608
5 014
12
1 067
2 279
3 618
5044
6 299
6 523
6544
7 041
7898
9 069
10 458
18 053
18 632
20100
20556
20279
20996
21 497
22 172
22 006
22 749
22 797
23 543
23 776
24 424
24783
24 631
24 752
6HI3 12
6F1I2
6HUI !
sFal!
6F6/!
6F m
6F 91!
6Fu/s
'G6/!
'Fa/!
'Gm
'[912
7 033
7900
9 075
10460
17 860
18860
20 010
20 600
4M15I2
'[UI2
'1 13/2
'F6/!
'Ml7/2
'G9/2
20977
21 562
22 129
22 850
'II6/Z
'MI9 /!
(6P, 'Ph12
'L 13 /2
'F7I!
23 784
24 560
eP812
'Ku/!
'M!lIs
'L15/2
24 532
t.E
(em-I)
24
13
7
-10
-30
-8
2
6
2
-193
228
-90
E pi!
(em-I)
36d
1 080 d
2 286d
3 608 d
5 00064006630
7 100
8000
9 200
10500
17 900
18900
20 050
44
-19
65
-43
20 800
21 100
21 600
22200
101
22 700
8
136
24 050
24 570
24 950
-220
25 650
'GU/2
'DU2
eP712
26750
'47/2
'Kla/2
'F9/2
'D3/t
('D,6Ph/!
'Hm
'KIS/!
'H 9/2
'D 7/2
('K, 'L) 1711
'49/s
'Hul!
'HIB !2
'G71!
'G 9/!
'G6/2
27 700
27700
28 250
29 100
29 100
30 200
'Pill
'Gu 12
2'6/2
'Pa/2
'P 6/!
2F5/S
4433
TRIVALENT LANTHANIDE AQUO IONS. I
31 550
32 800
33800
Eoal.b
(em-I)
46
1 080
2 290
3 624
5042
6397
6508
6641
7 131
7977
9 136
10 517
17 924
18 832
20014
20526
20627
21 096
21 650
22 098
22 370
22 706
22 966
23 902
24 101
24 562
24 775
24 999
25 177
25 224
25638
25 718
26 573
26 660
26 749
26 967
27 207
27 714
27 722
28 396
28 732
29 012
29 107
29 178
29 322
29 381
29 827
29 980
30 099
30232
31 093
31 349
31408
31 508
32 706
33 767
t.E
(em-I)
-10
0
-4
-16
-42
3
-11
-31
23
64
-17
-24
68
36
173
4
-50
102
-6
-51
8
-49
12
90
-14
-22
-146
88
-7
101
U(2)o
U(4)o
U(6)c
0.2062
0.0256
0
0
0.1939
0
0.1444
0.0332
0.0020
0.1962
0.1395
0.0240
0.0007
0
0
0.1364
0.2840
0.1429
0.0206
0.0006
0.0007
0.0952
0.3267
0.2649
0.0659
0
0.0043
0
0
0.4301
0.3413
0.0515
0
0
0.0025
0.0014
0.0307
0.0108
0.0228
0
0.0053
0.0028
0.0002
0
0
0.0096
0.0003
0
0.0027
0
0.0060
0.0010
0
0.0751
0.0002
0.0011
...v()
0
0.0002
0.0003
0.0004
0.0022
0
0
0
0.0004
0
0.0001
0
0
.....,0
0
0.0002
.....,0
0
0
0
0
0.0001
.....,0
0
0
.....,0
0.0001
.....,0
0.0013
0
0.0001
...v()
0
0
0
0
.....,0
0.0001
0.0002
...v()
42
94
33
0
0
.....,0
.....,0
...v()
...v()
0.0018
0.0005
0
",0
0.0030
0.0002
0
0.0010
0
0
0.0263
0.0081
0.0012
0.1684
0.0004
0
0
0.0001
0
0.0016
0
0.0005
0.0004
0.0251
0.0170
0.0006
0
0.0002
0.0005
0
0
0.0001
...v()
0.0006
0.0009
0.0002
0
.......,0
0
0.0136
0.0021
0.0005
...v()
0
0
.....,0
.....,0
0.0006
0.0375
.....,0
0
0.0005
0.0002
0.0004
0.0013
0
0
0.0003
0.0002
0
0
0
4434

TABLE
VII ( Continued)
SmH (aq)
SmH in LaCl s"

Enptl
(em-I)
S'L'J'
Eea",b
(em-I)
dE
(em-I)
E vtl
(em-I)
33800
2K18/2
'F9/2
2LI7/2
('I, 'Fh/2
2NU/2
'PII2
4F7/2
'1 u /2
2NU/!
'Fo/2
'110/2
'Fa/2
34600
36000
36 700
36 700
'[13/1
2Ml us
(IH, '[)m
('D, 'F)3/2
'Ful
37 600
38300
IKIS/t
'GU2
IHu/!
'MUll
'Dol!
39 250
'[U/2
'KII"
'Dill
42000
'G9/2
'028/1
'021/1
'Go/s
42900
'G7/1
'Kw2
('H, 'G)g/l
(1[, 'Hhlll
(II, 'Hh./I
('G, IH, 'H) nil
('G, 'H) 7/1
43 100
43800
'G9/2
('G, 'H, 'G) 7/1

'GeJl
I[a/I
'Gtlll
1L.7/1
46500
46500
46 500
'HIllS
'Hu/!
('P,'Dh/l
'Dill
tHIlil
47400
'L.6/1
(IF, 'P, 'Dh/I

'Hg/I
rms Deviation
119
a Reference 35.
b The parameters used to generate this set of levels are given in Table II.
U (A) - (tfJ U(A) >It'fl'.
II
II
E lob
(em-I)
33 825
34 061
34 357
34 591
35 385
35 718
35 785
36 053
36 238
36 520
36 586
36 586
36 757
36 982
37 487
38 270
38 803
38 949
39 057
39 188
40 417
40664
40 990
41 269
41 369
41 941
42 022
42 406
42 714
42 965
43 028
43 250
43 414
43504
43 845
44 237
44 832
45 269
45 615
45 801
46 123
46 370
46 500
46 554
46 669
47 127
47 307
47 843
47940
48 288
dE
(em-I)
-25
U(2)o
0
~
-53
114
-57
113
30
62
49
-65
-150
-45
0
-54
-169
93
0
.....,0
0
",,0
,....,,0
0
0
",,0
0
~
0
0
,....,,0
~
0
0
0.0001
0
0
.....,0
0
0
",,0
'"'-0
0
0
0.0016
0.0013
0
0.0003
0
0
0
0.0002
.....,0
",,0
",0
0
0
0
0
0
0.0002
.....,0
0
0
0
",,0
U(4)o
U(6)
0.0002
.....,0
0.0001
.....,0
.....,0
0.0003
0
0
,....,,0
0.0003
0
0
",0
0
0.0001
0.0004
0
0
0
0.0002
0
rvO
0
0.0002
,....,,0
0
0.0005
0.0003
.....,0
0
",0
0.0002
0
",,0
0.0001
0.0001
",,0
0.0002
0
0
0.0010
0.0025
0
0.0008
0.0006
0.0002
0.0008
",0
",0
0.0006
0.0006
.....,0
0.0001
0
0.0004
0.0005
0.0010
",,0
0.0010
0
0.0003
,....,,0
rvO
0.0001
0
.....,Q
.....,Q
,....,,0
.....,Q
0
0
.....,0
.....,0
0
0.0001
0
0
0
0.0006
.....,0
0.0015
0.0006
.....,Q
0.0006
~
0.0002
.....,0
0
.....,0
0.0002
.....,0
0.0002
.....,0
0
0
0.0001
.....,Q
0
.....,Q
80
d Assumed based on data for Sm'+ in LaCIa (Ref. 35).
e Based on data in Ref. 28.
4435

TABLE VIII. Energy-level assignments and matrix elements of U(~) for Dyl+ (aq).
Dya+ (aq)
Dy8+ in LaC)."
E ptl
S'L'J'
IHI5/2
IH 1312
IHU/2
IH9I2
I FU/2
IFS/!
6H 7I2
6H5/1
IF7I1
IFsl2
IFI/2
'GUll
'Fm
'111/2
'MU/2
'Kim
'MIDIS
(4P, 'D)a/2
'Pm
'11111
'P7/1
('M, '1)15/1
('F, 'Dh/l
'I 91t
'Gm
'PIII
tt.E
E ptl
(em-I)
(em-I)
(em-I)
(em-I)
52
3 517
5 835
7 667
7667
9 014
9 014
10 140
10 926
12 323
13 116
35
3480
5804
7 637
7663
9011
9099
10146
10 945
12 341
13 109
13 650
21056
21 956
23 288
25 640
25 539
25 562
25 627
26 374
26 832
27 038
27 728
28346
28 575
29 383
17
37
31
30
4
3
-85
-6
-19
-18
7
52d
3 517d
5 850
7 700
7 700
9 100
9 100
10200
11 000
12400
13 250
12
11
17
8
-30
13
-15
31
-25
-32
38
-93
-2
15
21 100
22 100
23400
25800
25800
40
3 506
5 833
7 692
7 730
9087
9 115
10 169
11 025
12 432
13 212
13 760
21 144
22 293
23 321
25 754
25 919
26 341
26 365
27 219
27 254
27 503
28 152
28 551
29244
29 593
29 885
30200
30 803
30 892
31 560
31 795
31 842
31 857
32 187
33471
33642
33 776
33 834
34 307
34311
34 398
34954
35047
35891
36432
36 524
36 794
37 103
37 230
37 435
37 807
38 031
38811
38860
39 127
20 963
21 954
23 303
28 326
29480
26400
27400
27400
27400
-20
28 550
97
29600
30 800
('G,2F)7I1
'KlD/1
'Dl/ 2
4GB"
(4L, 'K)I812
4M,W2
'Pllt
4H7/1
'Fm
(2K,ILh5/2
('G, 'PhiZ
('P, 'F)."
tt.E
(em-I)
4M17/1
('D, 'Ghll
'M,D/S
'HulS
'FilS
('K, 'Lhllt
'Dm
,H11I1
'G9/2
'Fill
'GU /2
, M,712
('G, 'Hh/2
'Kult
(4G, 'PhIl
Eo.lob
(em-I)
IFlit
'F 9/1
'116/2
b
E ... lo
33500
33900
34900
34900
35900
36 550
37900
38900
39 100
-44
-193
79
46
-119
35
181
146
-103
-1
7
-3
29
66
-54
-147
9
26
-131
40
-27
U(2)-
U(4)-
U(6)"
0.2457
0.0923
0
0.9387
0
0
0
0
0
0
0
0
0.0073
0.0004
0
0.0041
0
0.0109
0.0004
0
0
0.0001
0
0.0023
0
0
0
0
0.0032
0
0.0028
0
0
0.0004
0.0099
0
0.0060
0
0.0029
0
0
0.0016
0.0003
0
0.0001
0
0
0.0003
0.0001
0
0
0
0.0003
0
0
0.4139
0.0366
0.0176
0.8292
0.5736
0.0007
0
0.1360
0
0
0
0.0047
0.0003
0.0145
0.0768
0.0013
0.0102
0.0048
0.0166
0
0
",0
0.5222
0.0005
0
0.0003
0.0014
0
",0
0.0066
0.0001
0
0
0.0203
0.0100
0
0.0024
0.0661
0.0018
0.0007
0
0.0054
0.0088
0.0042
",0
0
0.0013
0.0001
0.0016
0
0.6824
0.6410
0.1985
0.2048
0.7213
0.0392
0.0026
0.7146
0.3452
0.0610
0
0.0295
0.0654
0.0003
0.0263
0.0248
0.0822
0.0935
0.1020
0.0448
0.0697
0.0074
0.0125
0.0009
0.0249
0.0003
0.0005
0.1095
0.0012
0.0002
0.0093
0
",0
0.0056
0.0016
0.0045
rvO
0
0.0001
0
0
"-'0
0.0016
0.0022
0.0041
0.0004
0.0075
0.0018
0.0001
0.0001
0.0040
0.0014
0.0006
0.0002
0
0.0002
0.0043
0.0007
0.0061
0.0091
4436

TABLE
VIII (Continued)
DyH in LaCla"
Dy3+ (aq)
EeIJltl
S'L'J'
(em-I)
Eoalob
(em-I)
t:.E
(em-I)
40 922
fJI6/'
41 050
41 035
15
41 700
41 596
104
U(2)o
U(4)o
0.0015
0.0002
0.0043
0.0001
0.0030
U(6)
~O
'4712
41 848
4F7/!
42 127
0.0021
0.0002
2Pm
42 807
0.0005
rms Deviation
56
See Table II. Footnote f.

b The 'parameters used to generate this set of energies are given in
Table II.
seven-parameter fit required estimates for some of these

parameters. However, this procedure did permit an
immediate, striking improvement of the fit, and predictions of transition energies and intensities which
were readily verified by reference to the observed spectrum.I4
Ho3+ (flO)
In this and in subsequent heavy lanthanides, all

excited levels in the ground-term multiplet were observed directly either in aqueous solution or in a molten
nitrate salt medium. Bands at 22 100 (5G 6) and 27 700
cm-I (3G 6 ) (Table IX) are known to be hypersensitive. 25
The absence of any large background corrections in
the ultraviolet range made it possible to assign several
transitions to relatively weak bands between 40000
and 50000 cm-I.
Er+ (f11)
A considerable amount of experimental work on the
energy level scheme of Er+ has been reported including a study of the free-ion spectrum.86 The published
assignments for Er8+ (free-ion), Er+ in LaF3,37 and
Er+ in LaCla 38 are given in Table X, together with
the results of a six-parameter fit to the data in each case.
The experimental and calculated results for Er8+ (aq)
are shown in Table XI. Practically all of the states
which would be strongly dependent on 'Y lie at > 50 000
cm-l . Only in solution was it possible to obtain an
estimate of the value of this parameter.
Tm3+ (f12)
In order to obtain experimental results in a crystal

medium that were comparable to those for Tm3+ (aq) ,
as w. J. Carter and H. M. Crosswhite, J. Chern. Phys. (to be
published) .
1fT W. F. Krupke and J. B. Gruber, J. Chern. Phys. 41, 1225
(1964) .
18 F. Varsanyi and G. H. Dieke, J. Chern. Phys.36, 2951 (1962);
G. H. Dieke and S. Singh, ibid. 35, 555 (1961).
0.0001
0.0002
86
u 0.) = (Il-'J II Uo.) IIljIJ')t.

d Assumed energy based upon data in Table II. Footnote f.
it was necessary to employ the data published by several different authors for Tm(C2H 5S04 )a-9H20,3lH2 as
shown in Table XII. Since the value of 'Y in this case
depends wholly on the energy assigned to the transition
to ISO, which has not been observed, it was necessary
to limit the fit to six parameters.
DISCUSSION
Intensity calculations have proven to be a useful

tool in the assignment of energy levels in lanthanide
solution spectra. The energy parameters summarized
in Table II for the aquo ions should also provide a
valuable guide to further assignments in crystals. Since
all three parameters of configuration interaction have
been determined here for the first time for trivalent
lanthanides, it now becomes possible to examine their
behavior across the series. We will also be interested
in the variation of the values of Flo and tv determined
here as a function of the atomic number Z. That part
of the configuration interaction which has the same
angular form as the coefficients, e", of the E" parameters [Eq. (6) ] provides a negative screening of the
E"'s which is not removed by the addition of a, (:1, and
'Y. This screening results in the empirical parameters
being smaller than those calculated by Hartree-Fock
(H-F) methods. 43
Slater Integrals (F,,)
A plot of F2 vs Z for the lanthanides considered here

is linear to a good approximation as shown in Fig. 1.
811 J. B. Gruber and J. G. Conway, J. Chern. Phys. 32, 1178
(1960); 32, 1531 (1960).
40 E. Y. Wong and I. Richman, J. Chern. Phys. 34, 1182 (1961).
41 B. C. Gerstein, L. D. Jennings, and F. H. Spedding, J. Chern.
Phys. 37, 1496 (1962).
42 W. F. Krupke and J. B. Gruber, Phys. Rev. 139, A2008
(1965) .
48 A. J. Freeman and R. E. Watson, Phys. Rev. 127, 2058
(1962) .
4437

TABLE IX. Energy-level assignments and matrix elements of U(~) for Ho3+ (aq).
H 0 3+ (aq)
Hos+ in LaCl3"
S'L'J'
51a
617
61d
610
61.
6F.
6S2
6F,
6Fa
6F2
3Ka
6GB
6FI
(SG,3G).
DG.
3K7
(sG,3H).
sHa
(6F, SF, 6Gh
iGS
sLg
(SF, 3H, 3G).
sKs
6G2
3Da
3PI
aM10
aLa
(6G, 6D, 3G),
(3F,3G)a
3PO
(3H, 6D, IG).
3F2
ILa
(3H,3G).
(3P,ID)z
E ptl
(em-I)
5
8
11
13
15
18
18
20
21
21
22
107.7
154.8
656.9
218.9
284.1
482.0
430.3
553.9
614.0
069.2
350.7
100.6
23
25
26
27
936.4
820.4
139.7
648.8
27968.8
28 810.6
28 911.4
33 066.5
34 728.3
36 722.2
3~
sh
38 314.2
3F.
31s
3Mp
31s
(3D, 6D, sPh
iD3
(3F,6D).
6D2
iDO
(SF,6D)a
6DI
(lD,3Dh
3Ma
3H.
(3H, II).
3F3
(3H, 3G, 31).
(ID,3Fh
IH"
rms Deviation
E ... lcb
(em-I)
140
5 169
8 668
11 216
13 272
15508
18 284
18 619
20644
21 058
21 310
22 118
22 304
23 782
25 798
26 114
27640
27 703
28 136
28 786
28 988
29 915
29 994
30 687
33 130
33 152
34375
34 273
34 761
34977
35 852
35 980
36 006
36488
36684
37 686
37 924
38 268
(em-I)
(em-I)
Ealcb
tJ.E
(em-I)
-32
-13
-11
3
12
-26
146
-65
-30
11
41
-17
108d
5 130
8 580
11 120
13 300
15500
18 500
18500
20 600
21 100
21 370
22 100
28
14
-34
-45
81
-19
146
-112
-73
-30
62
6
154
22
26
9
23 950
25800
26200
27700
27 700
28 250
28 800
29000
30 000
30000
30900
33 200
80
5 116
8 614
11 165
13 219
15 519
18 354
18 612
20 673
21 130
21 308
22 094
22 375
23 887
25 826
26 117
27 653
27 675
28 301
28 816
29 020
30 017
30 036
30 813
33 339
33 398
34264
34 306
34794
35 224
36050
36046
36 364
36 516
36773
37 845
38 022
38 470
38 509
39271
39 435
39 830
39 982
39 992
41 532
41 922
42 582
42 811
43 066
45 286
45 691
45 705
45 724
47448
48 102
48 736
49 335
AE
(em-I)
-167
24
-77
-64
-33
E.xp'l
34200
34200
34800
35200
36000
38
46
36500
36 800
38000
38500
38 500
39500
40000
41 550
41900
42 850
45 700
48200
~2
See Table II. Footnote g.

b The parameters used to generate this set of energies are given in
Table II.
Uo..) = (!/tJII U IA ) ,yJ/)
II
63
-26
83
47
25
-51
-16
-20
-17
-36
87
-139
-64
-106
6
-24
-46
-16
27
-22
30
-9
65
8
18
-22
39
-24
98
62
U(2)c
0.0250
0.0084
0
0
0
0
0
0
0
0.0208
1.5201
0
0
0
0.0058
0
0.2155
0
0
0.0185
0
0.0026
0
0
0
0.0003
0.0017
0
0
0
0
0
0.0002
0
0
0.0020
0.0157
0
0
0.0005
0.0065
0
0
0
0
0
0
0
0
......,0
0
0.0001
0
0
0
0
U(4)c
0.1344
0.0386
0.0100
......,0
0.4250
0
0.2392
0
0
0.0334
0.8410
0
0.5338
0.0315
0.0046
0.0790
0.1179
0
0
0.0052
0.1260
0.0002
0
0
0
0.0696
0.0005
0.3040
0
0
0.2635
0
0.0056
0.0024
0
......,0
0.0003
0.0084
0.0008
0.0057
......,0
0
0
0.2577
0
0
0
0
0
......,0
0.0068
0.0118
0
0.0034
0
0.0016
U(6)c
1.5216
0.6921
0.0936
0.0077
0.5687
0.2268
0.7071
0.3460
0.1921
0.1578
0.1411
0
0.0002
0.0359
0.0338
0.1610
0.0028
0.0041
0.0133
0.1536
0.0047
0.0026
0.0010
0.0030
0
0.0808
0.0108
0.0492
0.0036
0
0.0041
0.0035
0.0016
0.0032
......,0
0.0036
0.0080
0.0023
0.0008
0.0029
0.0043
0
0.0293
0.0144
0.0128
0
0.0079
0
0.0004
0.0001
0.0003
0.0005
0.0008
~
~
~
d Assumed energy based on data in G. H. Dieke and B. Pandy, J. Chern .

Phys. 41. 1952 (1964).
Based on data in Ref. 29.
4438

TABLE X. Energy-level assignments for E1"+.
---------- ====--===================
Er3+ (free ion)'
Er3+ in LaCl{
S'L'J'
96
-96
217
232
-15
108
130
-22
6 485.9
6 567
-81
6697
6 732
-35
6 589
6 630
-41
10 123.6
10 140
-16
10340
10 335
10219
10226
-7
12 345.5
12 294
61
12 567
12 504
63
12 438
12 377
61
15 182.9
15 202
-19
15 452
15 432
20
15 283
15 260
23
18 299.6
18 445
-145
18 570
18 696
-126
18 398
1~
536
-138
19 010.8
19 096
-85
19 334
19 398
-64
19 144
19 181
-37
20 494.1
20 391
103
20 709
20 652
57
20 515
20 449
66
22 181.8
22 014
168
22 378
22 305
73
22 174
22 097
77
22 453.9
22 368
86
22 711
22645
66
22 516
22 449
67
24 475.2
24 367
108
24744
24644
100
24 565
24 471
94
26 376.9
26 348
29
26 585
26 680
-95
26 367
26 397
-30
27 319.2
27 333
-14
27 629
27 693
-64
27 327
27 358
-31
27 584.9
27 597
-12
27 605
27 643
-38
27 825.0
27 843
-18
28 298
28 176
122
27 987
27909
78
31 414.4
31 496
-82
31 718
31 844
-126
31 497
31 625
-128
32 972.2
32 862
110
33 139-
33 145
-6
32 963
32 927
36
33 088.4
33 266
-178
33666
33 284
33 240.2
33 218
12
33 629
33 418
33 849.1
33 840
34211
34 209
33 944
33 921
23
34 733.3
34 534
199
35 055
35 010
45
34 755
34 743
12
36 479.5
36 326
144
36641
36 676
-35
36440
36501
-61
38 406.1
38 375
31
38 827
38 816
11
39 268.5
39 026
242
39 530
39 519
11
27 857
40 808
2111/2
41 438
41 854.7
42 028
-173
42 426.2
42 710
-284
43 507
46 829
47 420.0
rms Deviation
47 532
-112
141
Reference 36.
b Reference 37.
References 17 and 38.
d The parameters used to generate this set of energies are given in
Table II.
84
84
This energy was assigned to the transition to <G./. in Ref. 37. but intensity considerations suggest the indicated assignment.
f Not all of the Stark components of this level were observed.
ENERGY LEVELS OF TRIVALENT LANTHANIDE AQUa ION S. I
4439
TABLE XI. Energy-level assignments and matrix elements of U(~) for Er3+ (aq).
Ecalea
(em-I)
tiE
(em-I)
108e
109
-'-1
'IIaII
6600
6 610
'IUI2
10 250
'1 912
E..ptl
(em-I)
U(6)b
U(2)b
U(4)b
-10
0.0195
0.1173
1.4316
10 219
31
0.0282
0.0003
0.3953
12 400
12 378
22
0.1733
0.0099
'F.12
15 250
15 245
0.5354
0.4618
'Sill
18 350
18 462
-112
0.2211
2Hl112
19 150
19 256
-106
0.7125
0.4125
0.0925
4F712
20 450
20 422
28
0.1469
0.6266
'Fbll
22 100
22 074
26
0.2232
'Fall
22500
22 422
78
0.1272
(2(;, 'F, IH) 912
24 550
24 505
45
0.0189
0.2256
4{;1112
26400
26 496
-96
0.9183
0.5262
0.1172
'G 912
27400
27 478
-78
0.2416
0.1235
0.0219
0.0041
0.0758
S'[J]'
'11012
27801
2Klol 2
2(;711
28 000
27 979
21
0.0174
0.1163
(2P, 2D, 'F)all
31 600
31 653
-53
0.0172
'Kla12
33200
33 085
115
0.0032
0.0029
0.0152
'Go12
33400
33 389
11
0.0026
33 453
'Plil
'G 712
34 050
34 022
28
0.0334
0.0029
2Dal2
34850
34800
50
0.0228
(2H,2(;)912
36 550
36566
-16
0.0501
0.0001
2Dal!
38600
38 576
24
0.0267
'Dl/2
39200
39 158
42
0.8921
0.0291
211112
41 150
41 009
141
0.0002
0.0284
0.0034
2L1712
41 650
41 686
-36
0.0047
0.0664
0.0327
'D812
42300
42 257
43
0.0126
0.0002
0.0050
0.0170
0.0050
42966
(2D,'PhI2
43 550
'Ita/!
43 717
167
'DIll
47040
2H912
47 822
0.0038
0.0001
'LW2
47 916
0.0002
0.0026
0.0021
0.0096
0.0001
0.0082
(2D, 'Dhl!
2Hl11'
49000
49033
-33
51 000
rms Deviation
a The parameters used to generate this set of energies are !liven
in Table U.
~O
81
b U (X) = (1/;J II U (~) II 1/;' f)'.
o Assumed energy based on data in Ref. 38.
4440

TABLE XII. Energy-level assignments and 'matrix elements of U(}.) for Tm8+ (aq).
Tm (C2H~SO.) s 9H2O"
Eoalob
TmH (aq)
(em-I)
(em-I)
t..E
(em-I)
BH6
170
141
29
sF.
5 787
aH.
5846
8 250
aH.
12 665
BFa
14 464
BF2
15 192
E.xptl
S'L'J'
Eoal."
(em-I)
t..E
(em-I)
U(2)o
170d
202
59
5 900
5 811
-32
89
0.5375
0.7261
0.2382
8 326
-76
8 390
12 720
-20
0.1074
0.2373
0.1090
0.6383
0.5947
14 514
-8
-50
8400
12 700
0.2314
12 673
14500
14510
-10
15 112
80
15 100
15 116
-16
21 350
28000
21 374
-24
0.0483
0.0748
0.0125
28 032
34900
34 886
-32
14
0
0.0106
0.3156
0.0388
0.0928
0.0134
0
0
0.0756
0.1239
0.2645
0.0223
0.0002
IG.
21 300
21 306
-6
ID2
27 916
28 014
-98
19
lIs
34 870
34 851
BPO
35444
35 641
aPI
36 461
aP2
38 257
ISo
E oxptl
(em-I)
10
35 500
35 637
36 295
-197
166
36400
36 298
-137
102
38 175
82
38 250
38 193
57
79 592
79 720
U(6)'
0.3164
0.8411
0.2581
~O
94
143
rms Deviation
U(4)o
References 39-42.
b The parameters used to generate this set of energies are given
in Table U.
Using an equation of the same form as that given by

Satten,8 we obtain
F2 = 12.820(Z-34) ,
(8)
where a screening constant CT=34 is used in the expression for the effective nuclear charge (Z-CT).
o U (X) = (!f;J II Ul~) II !f;'JI),

d Assumed energy based upon data in Refs. 40 and 41.
The approximate values of F2 obtained from fourparameter fits to the data for Eu3+, Gd3+, and Tb3+ 14,15
lie well above the line determined by Eq. (8). Since
several'observed levels for each of these ions are strongly
dependen t on 'Y,'" the effect is probably a reflection of
the insensitivity of the low-lying levels to the values
of F 2 The H-F calculations of Freeman and Watson43
yield values of F2 that are, except for Pr3+ and Nd3+,
AT-
-----
r--'-'---;;r-'-'--'--'~::-'--'-'~2
-- __ -.........
/
41'hydrooenic rotio
'''''
0.017
0,015
0.013
F2
(eM")
0.011
400
0.16
0.14
F2 12.820 (Z-34)
350
-',-e----
.----_---3
__ .-
=--._._. ___ .______'.______ -:F4
4fhydrOQenic rotlo
F;
0.12
0.10r-
300~--~--~--L-~--~--~--~~--~--~
3 + Ho 3+ Er 3+ Tm 3+
Pr 3 + Nd 3+ Pm 3+- 5m 3'" Eu 3+ Gd 3+ Tb 3+
OV
(59)
16il
(63)
(65)
(67)
(59)
Pr 3 + Nd'+ Pm' 5m 3+
Eu'''' Gd 3+ Tb 3 + 0)'3+
Ha'
I
Er 3 + Tm'34-
(59)
(63)
(67)
(69)
(61)
(65)
ATOMIC NO, Z
ATOMIC NO. Z
FIG. 1. Variation across the lanthanide series of the parameter

F2 obtained from a fit to lanthanide aquo-ion data.
FIG. 2. Variation aeross the lanthanide series of the ratios

F4/F2 and Fs/F4 calculated from a fit of lanthanide aquo-ion
data.
ENE R G Y LEV E L S 0 F T R I V ALE NT LAN T HAN IDE A QUO ION S. I
4441
3000~--~---r--~--r--.--~---r--'---r--.---.--~,
2800
2600
2400
2200
FIG. 3. Variation across the lanthanide

series of the spin-orbit coupling constant,
calculated from a fit to lanthanide
aqua-ion data.
r".
1800
1600
1400
1200
1000
800
ATOMIC NO. Z
a linear function of Z with the same slope as that of

the present experimental results shown in Fig. 1. We
find the relationship F2 (H-F)::1.4 F2 [Ln3+ (aquo)],
where Ln3+ represents those lanthanides heavier than
Nd3+.
Values of F4/F2 as a function of Z are quite regular.
As shown in Fig. 2, the average is near 0.15 which is
somewhat larger than the ratios calculated assuming
that 4/ wavefunctions are hydrogenic [Eq. (4)] or by
using H-F methods (::0.130).43
There is an apparent change in the ratio F s/F 2 from
somewhat less than the hydrogenic ratio [Eq. (5) ] for
the light lanthanides to greater than this ratio for the
heavy members of the series (Fig. 2). Hartree-Fock
calculations give Fs/F2::0.0139.43 There is no obvious
explanation for this nonlinear variation in the experimental results, but the parameters are well-enough
determined to suggest that the effect is real.
Spin-Orbit Coupling Constant C!;4/)
The variation of !4/ across the lanthanide series is

shown in Fig. 3, where the values for Ce3+ 44 and Yb3+ 13
have also been included. A good approximation to the
values of this parameter14 can be obtained for Eu3+,
Gd3+, and Tb3+ even though the assignments to the
"R. A. Buchanan, H. E. Rast, and H. H. Caspers,
Phys. 44,4063 (1966).
J. Chem.
experimental data are limited to components of only

two or three different multiplets.
Attempts were made to express !41 both as a linear
and as a quadratic function of Z. At the outset it was
clear that the average deviation from the experimental value was appreciably increased when the data for
Ce3+ and Yb3+ were included, regardless of whether
the expression was quadratic or linear. Results excluding Ce3+ and Yb3+ showed that the average deviation
was appreciably less when two linear functions with a
common value at Gd3+ were employed as compared to
a single quadratic function. The linear functions were
!4/=142Z-7648 (Pr3+ through Gd3+) , average devia tion from exptl = 11.3,
!4/=231.142Z-13330.3 (Gd3+ through Tm3+) , average deviation from exptl=9.5.
Spin-orbit coupling constants for most of the trivalent lanthanides have been calculated by Blume,
Freeman, and Watson, using analytic nonrelativistic
H-F functions. 46 These authors have discussed at length
the fact that the calculated coupling constants are
larger than those obtained experimentally. We found
that the calculated values only differ from those given
in Fig. 3 by a scaling factor. Two linear functions of Z,
"M. Blume, A. J. Freeman, and R. E. Watson, Phys. Rev.
134, A32 (1964).
4442

40
,0
20
/0
0
-\7
/20
I
80
::;;
<.)
-fJ/12
-\:=t_~Il
40
0
6000
4000
2000
~!--I
0
Pr Nd Pm Sm Eu Gd Tb Oy Ho Er Tm
(59)
(61)
(63)
(65)
(67)
(69)
ATOMIC NO. Z
FlG. 4. Variation across the lanthanide series of the configuration-interaction parameters a, {3, and l' calculated from a fit to
lanthanide aquo-ion data.
in these parameters as a function of Z in the 4fN series

is much greater than that observed in the dN series.
We note that in general, the magnitude of {J/l2 is
approximately twice that of a.
Where it was possible to define a value for 'Y, we
found it to be positive, and the average was near
1100-1200 em-l. The only previous determination of
'Y was from the free-ion spectrum of Pr2+, and in this
case a negative value for the parameter was obtained. 24
The latter result depended upon only one somewhat
doubtful level.
In view of the present results, a negative value for
'Y in Pr2+ seems very unlikely. It is highly probable
that the 2F6f2 level from which the value of 'Y was
determined is spurious. This view is further supported
by the calculation of Trees22 which indicated that 'Y
should be positive.
Recent H-F calculations for Pr2+ show that the major
contribution to 'Y comes from interaction with 4d84f6.48
Although there are negative terms arising from interaction with configurations such as 4f6p and 4p64f4,
these are not sufficient to overcome the large positive
contributions from 4d84f5.
CONCLUDING REMARKS
having the same slope as those of Fig. 3, but with a

common value at Eu3+ instead of Gd3+, give an excellent
fit to the H-F data.
Configuration-Interaction Parameters (a, {J, 'Y)

The systematic behavior of the configuration interaction parameters has been studied previously only in
the 3dN and 4dN configurations. By assuming that each
of the parameters follows an equation of the form
where x=N-6 and y=x2-l0, Shadmi46 ,47 was able

to fit simultaneously the energy levels of an entire
series by the determination of only the "general parameters," Ai. In doing this he assumed that a and {J
vary linearly with N, i.e., A 2 =O. However, if one compares the values of ex obtained on the basis of this
assumption with those obtained as a result of individual
fits to the levels of a single ion, there are frequently
large differences well outside the rms deviation of the
parameters. 47 Thus, a linear variation of a with N is
not apparent in the case of the single-ion fits.
In the case of the lanthanides, the absolute magnitudes of a and {J appear to increase in the first half of
the series after Pr3+, and decrease in the second half
(Fig. 4). It is clear that the magnitude of the variation
46
47
Y. Shadmi, Phys. Rev. 139, A43 (1965).

y. Shadmi, J. Res. Nat!. Bur. Std. A70, 435 (1966).
At present it is possible to compare the solution parameters determined here with those of the free-ion
only for Pr+ and Er+. l9 ,36 One would expect covalent
bonding effects in solution to reduce the parameters
slightly from those obtained for the free ion. The reduction is about 5% for the Ek and t41 values of Pr+.
The configuration-interaction parameters are somewhat
more sensitive. The Ek and t4/ values for Er+ are
slightly higher for the solution than for the free ion,
while a and {J are lower. However, the rms errors on
the parameters are nearly the same as the differences,
so the effect may not be significant. We would expect
the present results to provide a good starting point for
further analyses of both the crystal and free-ion spectra of 4JN configurations.
ACKNOWLEDGMENTS
We gratefully acknowledge the large contribution of
B. G. Wybourne, University of Canterbury, Christchurch, New Zealand, which made much of this work
possible. We would also like to thank F. L. Clark, C.
Chamot, and S. Katilavas for their assistance in programming and carrying out the computer calculations.
We are indebted to J. G. Conway and T. Clements,
Lawrence Radiation Laboratory, University of California, for providing us with a number of computer
programs and tapes used in this work.
48 M. Wilson and K. Rajnak (pri vate communication, November
1967) .

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Electronic Energy Levels in the Trivalent Lanthanide Aquo Ions. I.

Additional information on J. Chem. Phys.

T'HE JOURNAL OF CHEMICAL PHYSICS

VOLUME 49, NUMBER 10

Electronic Energy Levels in the Trivalent Lanthanide Aquo Ions.

Chemistry Division, Argonne National Laboratory, Argonne, Ininois

In 1907, BecquereP first showed that the absorption

trum of Nd3+ in Nd(Br03)s9H20 by Satten in 19538

* Work performed under the auspices of the U.S. Atomic

G. H. Dieke, Advances in Quantum Electronics, J. R. Singer,

ENERGY LEVELS OF TRIVALENT LANTHANIDE AQUO IONS. I

example see Refs. 15 and 16), only the general outline

In Eq. (2), the electrostatic energy (Ee) is expressed

16 J. P. Elliott, B. R. Judd, and W. A. Runciman, Proc. Roy.

As Wybourne16 has pointed out, this approximation

X' =aL(L+ 1) +/1G(G.!) +yG(R7 )

where a, /1, and 'Yare linear combinations of radial

CARNALL, FIELDS, AND RAJNAK

lated to the correction (3Q used by Racah23 and Trees. 22

G. Racah, Phys. Rev. 85, 381 (1952).

to small variations in Fk and t4j. Thus, it appeared

ENE R G Y LEV E L S 0 F T R I V ALE N T

In this section we will discuss some of the individual

LAN T HAN IDE A QUO ION S. I

TABLE~. Comparison .between the centers of gravity of levels

each case, the literature was searched for the results

23. 138O .15

Reference 20; G. H. Dieke and B. Pandy.

J. Chern. Phy 41, 1952 (1964).

J. Chern. Phys. 35,1535 (1961); J. D. A1ce and G. H. Dieke,

ENERGY LEVELS OF TRIVALENT LANTHANIDE AQUO ION S. I

TABLE III. Energy-level assignments for Pt'+.

Pt'+ Free ion a

d The parameters used to generate this set of energies are given in

found that where comparison is possible lanthanide

The parameters used to generate t "i. set of energies are given In

-(,yJ II U().) ",y'J')I.

Assumed energy based on data in Ref.

d Based on data in Ref. 28.

FIELDS, AND RAJN AK

V. Energy-level assignments and matrix elements of U(X) for NdH (aq).

in Table II for all the systems examined. The values

H. Caspers, H. E. Rast, and R. A. Buchanan, J. Chem.

Phys.43, 2124 (1965).

U (1\) = (1/11 II u(X) 11.p'J') t.

particularly relevant. The assignments, together with

ENERGY LEVELS OF TRIVALENT LANTHANIDE AQUO IONS. I

determine the value of the configuration-interaction

A comparison of the energies for Nd3+ transitions in

A center for the Stark components of the ground

Inorg. Nuc!. Chern. 14,

only three had large matrix elements of U(A): 5Do, 5DI ,

The energies of the 6FI / 2 and 6Fs/2 levels in Sm3+ were

Chern. Phys. 37, 2354

CARNALL, FIELDS, AND RAJN AK

included in the fit. As we extended the earlier study

Assumed center of Stark components of the ground level.

energies, the error was 200-300 cm-1 in a number of

TRIVALENT LANTHANIDE AQUO IONS. I

CARNALL, FIELDS, AND RAJNAK

SmH in LaCl s"

('G, 'H, 'G) 7/1

(IF, 'P, 'Dh/I

ENERGY LEVELS OF TRIVALENT LANTHANIDE AQUO IONS. I

=--._._. _ .'.__ -:F4