Structure of the f6 Configuration with Application to RareEarth Ions

G. S. Ofelt

Citation: J. Chem. Phys. 38, 2171 (1963); doi: 10.1063/1.1733947
View online: http://dx.doi.org/10.1063/1.1733947
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S P E C T R 0 S COP Y 0 F POL Y N U C LEA R A ROM A TIC H Y D ROC ARB 0 N S. I 2171
ACKNOWLEDGMENTS
One of us (RSB) wishes to gratefully acknowledge
the generosity of the donors of many of the com-
pounds studied in this investigation. In particular,
Professor M. Newman, of Ohio State University,
maintained a patient and unwavering attitude at each
"last" request. Also, Professor L. Fieser, of Harvard
University, and Professor R. Elderfield, of the Uni-
THE JOURNAL OF CHEMICAL PHYSICS
versity of Michigan (curator of the samples of the
late Professor Bachman) for allowing several days of
digging into the cigar-box treasures. Without the co-
operation of these and other sources, this effort could
not have been successfully accomplished.
We are also thankful to Mr. J. Michael Tadlock for
help in preparing the solutions, recording the spectra,
and plotting the curves.
VOLUME 38, NUMBER 9 1 MAY 1963
Structure of the 1
6
Configuration with Application to Rare-Earth Ions*
G. S. OFELT
The Johns Hopkins University, Baltimore, Maryland
(Received 14 December 1962)
Free-ion energy-level schemes for the 4f6 and 41
8
configurations of Eu'+, Sm2+, and Tb3+ are given, which
have been calculated from energy matrices including interactions among the three highest multiplicities.
The values obtained for the parameters are F2 = 401 em-I, r = 1320 cm-
I
for Eu3+; F2 = 330 em-I, r =
1050 cm-
I
for Sm2+; and F2 = 434 em-I, r = 1705 cm-
l
for Tb3+. The wavefunctions and g values for levels
to 40 000 cm-
l
are tabulated for Eu3+ and Tb3+. Application of the free-ion wavefunctions to the Stark
splitting of EuCh and TbCh is discussed.
I. INTRODUCTION
T
HE knowledge of the theoretically computed en-
ergy levels of configurations containing several 4f
electrons has proven the greatest single aid for the
analysis of the very complicated free-ion emission
spectra of the rare earths, and, therefore, such calcu-
lations have been undertaken in our laboratory for
several key configurations. The 4jn configurations are
also of importance for the interpretation of the crystal
spectra of the rare earths and have been studied in
recent years by a number of investigators.
In this paper, calculations on the equivalent 4j6 and
41
8
configurations are reported, which are of direct
importance for the crystal spectra of Eu3+ and Tb3+
as well as Sm
2
+ and Gd
H
. The number of multiplets
for this configuration is 119, which, through spin-orbit
interaction, give rise to 295 levels characterized by
the quantum numbers aLS J, where a signifies any
set of quantum numbers required to differentiate be-
tween different levels with the same values of L, S,
and J. Therefore, the spectra originating from transi-
tions between the Stark components of the various
aLSJ levels within the 4f6 configuration of Eu3+ (or
the 41
8
configuration of Tb
3
+) should be expected to
be more complicated than that of the trivalent ions
nearer the ends of the rare-earth series. This complex-
ity is apparent from experimental investigations of the
crystal spectra of these two ions. It is hoped that the
* This work was carried out with the partial support of the U. S.
Air Force Office of Scientific Research.
results of the calculations presented here will provide
an aid to further experimental analysis.
II. FREE-ION ENERGY CALCULATIONS
The theory for the free-ion energy-level calculations
has been known for some time and we shall consider
the usual perturbation Hamiltonian consisting of the
electrostatic and spin-orbit interactions. Then, the
matrices of interest are the coefficient matrices of the
radial integrals Fk and r, respectively.l
The electrostatic interaction between states of the
f6 configuration has been calculated by Wybourne
2
and,
also, independently by Gruber.3 It has been pointed
out that, for the rare-earth series, reasonable agree-
ment of the calculated and experimental energy levels
requires, in general, the inclusion of the spin-orbit
interactions with the states of the next lower and higher
spins than those of the multiplet of interest.4 In the
case of Eu3+ and Tb3+, if the quintet states are included
in the energy-level calculations, reasonable agreement
for the levels of the 7 F mUltiplet is obtained, but not
for the levels of the lowest 6D mUltiplet. Therefore,
the triplet states have been included for the spin-orbit
interaction matrices. The septet-quintet-triplet spin-
orbit matrix elements were calculated
5
with the help
I G. Racah, Phys. Rev. 63, 367 (1943); 76, 1352 (1949).
2 B. G. Wybourne, J. Chern. Phys. 35, 340 (1961).
'J. B. Gruber, UCRL-9203 (1961).
4 B. G. Wybourne, J. Chern. Phys. 36,2295 (1962).
5 G. S. Ofelt, dissertation, The Johns Hopkins University, 1962.
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2172 G. S. OFELT
40 XIOOOcm-1
'K
~
'p
'K
oK
Eu IV
.2.-_'F
'F
" "
"
'F
'F
'F
~ " 401 em1
"
"
t '320 em"'
'H 'H
'H
'H
--'H
30
'0
'L
'G 'G 'G 'G
'G 'L
'L
'L
'0 'L --
'0
20
'0
'0
r---
10
o 'F
o 2 3 4 5 J 6 7 8 9 10 II 12
FIG.!. Energy levels of Eu
3
+ below 40 000 em-I.
of the relationships given by Wybourne.
6
The energy
matrices (even excluding the singlet states) become
rather large-38th order for the J = 4 manifold-and,
therefore, the diagonalization process was carried out
with the aid of an IBM 7090 electronic computer,
using a program developed here,
4
providing the energy
levels and eigenvectors for the free-ion problem. The
effect on the energy-level scheme caused by neglecting
the interactions with the singlet states is discussed in
the following section.
The assumption of hydrogenic ratios for the Slater
integrals Fk has proven satisfactory for the 4fn con-
figuration of the triply ionized rare-earth elements and
has been used in the calculations reported here.
A. 4f6 Configuration of Eu3+
The published data on Eu3+ crystal speC'tra are
rather sparse-
7
F multiplet and lower levels of the
5D multiplet. However, with the help of the experi-
mental data of DeShazer and Dieke,1 the parameters
F2 and r were adjusted to give reasonable agreement.
The values obtained are 401 and 1320 em-I, respec-
B. G. Wybourne, J. Chern. Phys. 35, 334 (1961).
7 L. G. DeShazer and G. H. Dieke, J. Chern. Phys. 38, 2190
(1963) .
tivelYi and are 11 % higher and 3% lower, respectively,
than the values obtained from the empirical formulas
given by Judd and Lindgren.
8
The larger value of F2
is not too surprising, as it has also been observed for
Gd3+.4
An energy-level diagram is given in Fig. 1, including
the levels up to 40000 cm-
I
above the ground state
7 Fo, which includes the region of current experimental
interest, although the extent of the entire 4j6 configu-
ration is of the order of 190000 em-I. Tabulated values
for the energy levels and g factors for these levels are
given in Table I. The septet and quintet composition
of the eigenfunctions are given in Table II, with an
index to the Wand U classification of states given in
Table III.
Inspection of Fig. 1 clearly indicates the complexity
of the energy-level scheme. Above the 5D3 level there
is a rather dense group of levels comprised of the 5G
and 6 L multiplets as well as the 5 D4 level. Immediately
above this group is the rather isolated 6B multiplet,
followed by a very complex grouping of the 5F, 51, and
6K multiplets also containing the first triplet 3 P.
TABLE 1. Energy levels of the 4/" configuration of Eu3+ below
40000 em-I.
Energy Energy
(em-I) g value Label
(em-I)
g value Label
0 7FO 30 483 0.578 5H3
374 1.500 7FI 30 729 1.257 5H7
1 036 1.498 7F. 30 941 0.932 5H.
1 888 1.498 7F. 30964 1.142 5H5
2866 1.497 7F. 31 248 1.191 5H.
3 921 1.496 7F6 33 616 0.908 5h
5 022 1.495 7F. 33 870 0.679
51,
17 374 5Do 33 871 0.993 5F.
18 945 1.495
5D
I
33 955 1.228 5F3
21 508 1.492
5D
2
34 085 0.044
5F
I
24 456 1.487 5D, 34440 1.283 5F,
24 489 0.723 5L6 34 457
3P
o
25340 0.917 5L7 34 805 1.238 51a
26220 1.044 5La 34 919 1.086 51.
26 564 0.356 5G. 34 932 1.365 5F.
26600 0.860
5G
3
34 947 1.183 6Ir
26 725 1.095 5G. 36 179 0.739 5K5
26 733 1.191
5G
5
37 040 1.486 'PI
26 959 1.131
5L
g 37 573 0.944 5K.
27 065 1.293 5G. 38809 1.067 5K7
27 386 1.194 5LlO 39 508 1.153
6K
a
27 747 1.476
6D,
a B. R. Judd and 1. Lindgren, Phys. Rev. 122, 1802 (1961).
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i
6
CONFIGURATION OF RARE-EARTH IONS
TABLE II. Eu
s
+ eigenfunctions.
iD" iF'
iH' iI iI'
0.9680 0.0016 0.1659 -0.1815
0.9742 -0.0027 0.0052 0.1472 -0.1645 0.0263 0.0162
0.9819 0.0005 -0.0035 0.0108 0.1161 -0.1353 0.0452 0.0289
-0.0025 -0.0147 0.0172
0.9859 -0.0036 0.0180 0.0863 -0.0953 0.0659 0.0499
-0.0327 -0.0327 0.0309 0.0219 0.0020
0.9897 0.0126 0.0428 -0.0594 0.0751 0.0435
-0.0028 -0.0057
0.9880
-0.0405
0.9825
-0.0847
0.0591 0.0039 0.0055 -0.0004 -0.0002
0.0723 0.0392
0.0886 0.0075 0.0096 -0.0010 -0.0005 0.0001
2173
'L
-0.0676 -0.1201 0.1228 0.0094 0.0106 -0.0014 -0.0006 -0.0014 -0.0001
6D
o
b -0.2381 -0.1969 0.6893 -0.5390
6D
l
-0.2096 0.0012 -0.2066 0.7162 -0.5561 -0.0536 -0.0373
6D. -0.1624 0.0037 -0.0054 -0.2104 0.7456 -0.5742 -0.0888 -0.0724
-0.0155 0.0014 0.0038
6D
s
-0.1085 -0.0094 -0.2036 0.7509 -0.5826 -0.1330 -0.0881
-0.0437 -0.0252 0.0196 0.0146 0.0017
5D, -0.0401 -0.1754 0.7419 -0.5783 -0.1716 -0.1016
0.0107 0.0656 -0.0682 -0.0544 -0.0542 0.0191 0.0052
6F
l
-0.0500 -0.0199 0.0760 0.0161 -0.0779 0.8277 0.5080
of. -0.0787 0.0116 -0.0556 0.1105 0.0422 -0.1328 0.7830 0.4904
0.2009 0.0011 0.0292
6F
s
-0.0953 -0.0296 0.1140 0.0661 -0.1583 0.7599 0.4704
0.2542 -0.0381 0.0761 -0.0837 -0.0197
5F, -0.1023 0.0745 0.1018 -0.1709 0.7615 0.4457
0.2538 -0.0888 0.1251 -0.1350 -0.0348 -0.0634 -0.0161
6F5 -0.0911 0.8221 0.4245
0.1908 -0.0989 0.1336 -0.1386 -0.0146 0.0133 0.0007 -0.0318
0.0227 -0.0003 0.0023 -0.0065 0.0151 -0.0060 -0.0432 -0.0206
0.4750 0.6171 -0.5796
6G
a 0.0429 -0.0014 -0.0173 0.0515 -0.0342 -0.0551 -0.0163
0.4376 0.5752 -0.5340 -0.2932 -0.2583
6G, 0.0824 0.0185 -0.0775 0.0634 -0.0119 0.0178
0.4445 0.5345 -0.4998 -0.3595 -0.3024 0.0948 0.0272
6G
o
0.1103 -0.0220 0.0061
0.4358 0.4887 -0.4465 -0.4349 -0.3555 0.0733 0.0322 -0.0221
6G
6
0.1589
0.5089 0.4845 -0.4201 -0.3785 -0.2799 0.1462 0.0352 -0.0344 -0.0512
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2174 G. S. OFELT
Table II (Continued)
~ a t e s .
0p
6D'
Level", C'
6H' 5J 5J'
Ha 0.0110 -0.0014 -0.0014 0.0170 -0.0146 0.0131 0.0181
0.2622 0.2328 -0.1925 0.6795 0.5825
6H4 0.0243 -0.0027 0.0346 -0.0307 0.0307 0.0310
0.3293 0.2762 -0.2221 0.6048 0.5146 -0.3158 -0.0791
6H6 0.0506 0.0723 0.0566
0.4133 0.3243 -0.2521 0.5872 0.4682 -0.1599 -0.0610 0.0595
6H6b
0.0728
0.3171 0.2765 -0.2119 0.5022 0.4546 -0.4162 -0.1160 0.0819 0.0616
6H7 0.7206 0.4941 -0.4199 -0.0754 0.1050 0.0463
J4
-0.0079 0.0079 0.0112 -0.0183 0.0809 0.0490
0.0671 0.0257 -0.0080 0.2517 0.1870 0.8880 0.1802
610 0.0023
0.0054 0.0250 -0.0159 0.0426
6le 0.0110
0.0723 0.0530 -0.0278 0.4235
J7
0.3871
Ig
oK6
b
-0.0015
0.0023 0.0103 -0.0071 0.0090
oKa 0.0015
0.0311 0.0074 0.0011 0.0157
oK7 -0.0199
Kg
oK9
oLa 0.0051
0.0147 0.0136 -0.0118 -0.0216
-0.0147
6LIO
See Table III for classification of states.
b Eigenfunctions containing 10% or more triplet composition.
Although the calculations place the 5 Ls level 33 cm-
I
above the 5Da level, if we consider the effect of ccn-
figuration interaction expressed in terms of the factor
aL(L+l) introduced by Trees,9 we should expect the
former to lie at a higher energy relative to the latter
by an amount on the order of 10
8
em-I.
9 R. E. Trees, Phys. Rev. 83, 756 (1951).
0.0105 0.0041
0.0537 0.8600 0.1859 -0.3431
0.2399 0.7517 0.1433 -0.3536 -0.0606
0.2184 0.8141 0.1391 -0.2838 -0.0267
0.9338 0.1494 -0.2297 -0.0697
0.0307 0.0155
-0.0589 0.3753 0.0199 0.8307
0.0043 0.3979 0.0020 0.8475 0.0816
0.0056 0.3006 -0.0396 0.8995 0.1427
0.2186 -0.0189 0.9351 0.0923
0.9763 0.1024
-0.0184 0.0324 0.0075 -0.0942 0.9715
-0.0116 0.0168 0.0056 -0.1238 0.9765
0.0300 0.0130 -0.1260 0.9815
-0.1067 0.9817
0.9717
Although deviations from the Lande interval rule
are quite apparent for the 5 L multiplet, inspection of
the diagram clearly indicates stronger departure from
Russell Saunders coupling in the 5G multiplet. For
I> 2 the 5G
J
levels have strong admixtures of 5H, as
may be seen from the compositions as tabulated in
Table II. This departure from Russell Saunders cou-
pling persists for the majority of the excited levels,
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1
6
CONFIGURATION OF RARE-EARTH IONS 2175
especially since the admixture of triplet states becomes
increasingly large above approximately 34000 cm-
I
.
At greater energies, the admixtures in many cases
become very severe.
The effect of neglecting the singlet states in the
calculation of the energy matrices may be estimated.
We find from a calculation with no spin-orbit inter-
action that the lowest-lying singlet level is in the
neighborhood of 45 000 cm-
I
above 7 Fo. This has pre-
40 X 1000 em-'
'1' ..,.--
- - ~ ~ ~ "J _"_,
"F -- ",
- ~ --I,
_"_H_ "H
- ~ I H
, --
'0
,-:;- "0 ~
30 -i "6 "L "L
"0 -- '0' ----"L
--- - - ~ ' G -I
L
"0
"0
20
10
Tb IV
Fz' 434 ... -'
t '705.,.-'
'L
o ~ - - - - - - - - - - - - - ~ ~ - - - - - - - - - - - - - - - - - -
o 2 3 4 5.167 8 9 10 II 12
FIG. 2. Energy levels of Tb
3
+ below 40 000 em-I.
viously been reported by Gruber and Conway.lO Since
the singlet states only interact with triplet states
(spin-orbit interaction), the perturbation of levels not
containing an appreciable percentage of triplet states
-all levels below 40000 cm-
I
with the exception of
the 3 P multiplet itself-should be very small.
Therefore, it is expected that the calculations pre-
sented here should provide a reasonable description of
the energy-level scheme for the lower-lying excited
levels, subject to the acquisition of subsequent experi-
mental data, at which time the data would be suffi-
cient to obtain a final adjustment of the parameters
F2 and t.
TABLE III. Classification of states for Tables II, V, and VIII.
Notation W U 28+1L Notation W
U 28+IL
IF'
(100) (10)
(111) (00)
(210) (11)
(210) (20)
(210) (21)
(111) (20)
(210) (21)
(111) (10)
(210) (20) &G
(210) (21) IG
IG" (111) (20) IG
(210) (11) IH
(210) (21) 6H
(210) (20) 6]
(111) (20) I]
(210) (21) 6K
6 L (210) (21) I L
B. 4jS Configuration of Tb3+
The published data of Tb3+ crystal spectra are even
more sparse than those for Eu3+. With the aid of the
experimental data of Thomas, Singh, and Dieke,ll
reasonable agreement of the calculated levels with the
experimental levels was obtained for the values of the
parameters F
2
=434 and t= 1705 cm-
I
These values,
also, differ from those obtained from the empirical
TABLE IV. Energy levels of the 4f8 configuration of Tb
a
+ below
40000 em-I.
Energy
(em-I)
o
2 020
3 279
4 258
4 947
5 405
5632
20 455
25 760
26 216
27 263
27 312
27 659
27 982
28 183
28365
28720
28 920
28960
29411
Energy
g value Label (em-I)
1.493
1.495
1.496
1.495
1.497
1.497
1.489
1.193
1.482
1.290
1.132
1.192
1.483
1.047
1.094
0.931
0.744
0.883
0.359
30400
30 953
31 649
32 713
32 995
34107
34 414
35 315
35 628
36 223
36248
37009
37 201
37 563
37 780
37 791
37 939
39 295
39 473
g value Label
1.475
1.252
1.203
1.159
0.917
0.560
1.233
1.368
1.314
1.176
0.929
1.240
1.060
0.680
1.092
0.061
1.448
1.213
10 J. R. Gruber and J. G. Conway, J. Chern. Phys. 34, 632 11 K. S. Thomas, S. Singh, and G. H. Dieke, J. Chern. Phys.
(1961). 38, 2180 (1963).
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2176 G. S. OFELT
TABLE V. Tb
3
+ eigenfunctions.


51
0.9726 -0.0343 -0.1366 0.1800
0.9728 -0.0060 -0.0343 -0.1416 0.1661
0.9732 -0.0011 -0.0079 -0.0237 -0.1343 0.1603 -0.0697 -0.0378
0.0154 0.0205 -0.0159
0.9754
0.0266
0.9770
0.0404
0.9848
0.0535
0.9786
0.0617
0.2144
0.2128
-0.0061 -0.0075 -0.1221 -0.1368 -0.0908 -0.0521
0.0366 -0.0351 0.0033 0.0027
0.0061 -0.1048 0.1060 -0.0959 -0.0576
0.0613 -0.0637 0.0050 0.0065 0.0002 0.0001
-0.0770 -0.0483
0.0948 -0.0978 0.0001 0.0083 0.0040 0.0002
0.1329 -0.1401 0.0113 0.0157 0.0095 0.0023 0.0001
-0.1163 0.6870 -0.5670
0.0311 -0.1208 0.6756 -0.5530 0.1012 0.0466
0.2019 0.0142 0.0484 -0.1284 0.6493 -0.5220 0.1084 0.0689
-0.0504 -0.0213 0.0143
0.1950
-0.0741
0.1591
-0.0638
0.0203
0.0178 -0.1999 0.7465 -0.5573 0.1311 0.0883
-0.0297 0.0280 -0.0259 0.0045
-0.2183 0.7388 -0.5696 0.0727 0.0621
0.0028 -0.0466 -0.0050 -0.0016 0.0128 0.0082
-0.0142 -0.0253 -0.0731 0.1089 0.8733 0.3975
0.0536 -0.0284 -0.1003 -0.1581 0.0448 0.0943 0.8047 0.4086
-0.0799 0.0731 -0.0956
0.0517
-0.1267
0.0620
-0.1367
0.0679
-0.2148
-0.0496 -0.1041 -0.1118 0.1984 0.7993 0.4439
0.1311 -0.1578 -0.0746 0.0059
-0.0879 -0.0916 0.1673 0.7528 0.4581
0.1800 -0.1982 -0.1423 -0.0063 -0.1076 -0.0341
0.7593 0.4885
0.1516 -0.1699 -0.1829 -0.0304 -0.0071 -0.0093 0.0011
6(h. -0.0159 0.0012 0.0048 -0.0011 0.0395 -0.0366 -0.0078 -0.0213
0.6342 0.5657 -0.4600
6G
s
-0.0369 0.0067 -0.0153 0.0909 -0.0705 0.0022 -0.0217
0.5760 0.5347 -0.4520 0.2846 0.1805
IG. -0.0830 -0.0117 0.0473 -0.0346 0.0134 -0.0299
0.5052 0.5086 -0.4522 0.3745 0.2729 0.0869 0.0194
iG
5
-0.1139 0.0589 0.0168
0.4139 0.4697 -0.4381 0.4578 0.3593 0.0810 0.0261 0.0201
IG
6
-0.1800
0.3908 0.5194 -0.4970 0.3183 0.3204 0.1273 0.0491 0.0317 0.0877
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1
6
CONFIGURATION OF RARE-EARTH IONS 2177
Table V (Continued)
.
~ s a
7F 5S
5p 5D 5D' 6D" 5F 5F'
Level
6G 5G' 5G" 5H 5H' 51 51' 5K 6L
5Hs 0.0180 -0.0054 -0.0012 -0.0222 0.0242 0.0547 0.0412
-0.2301 -0.1891 0.1450 0.7839 0.4870
5H. 0.0471 -0.0058 -0.0384 0.0425 0.1248 0.0853
-0.3266 -0.2483 0.1855 0.6117 0.4245 0.4070 0.0720
5H
o
b
0.0910 0.1090 0.0883
-0.3540 -0.3669 0.3104 0.5473 0.4253 0.1533 0.0436 0.0286
5H6 0.0758
-0.2654 -0.2684 0.2319 0.5848 0.4512 0.4234 0.0931 0.0747 -0.0676
5H7 0.6726 0.5946 0.3481 0.0832 0.0738 -0.1323
51. -0.0075 0.0001 -0.0008 0.0016 0.0085 0.0018
0.0386 0.0758 -0.0567 -0.3900
6/0 -0.0098
-0.0368 0.0318 -0.0284 -0.1890
516 -0.0125
0.0742 0.0559 -0.0345 -0.3822
617 -0;2839
Is
5K
g
5Lob
0.0245
-0.0617 -0.0773 0.0692 -0.0170
5L7 0.0720
5Ls
Lg
5LiO
a See Table III for classification of states.
b Eigenfunctions containing 10% or more triplet composition.
formulas previously mentioned by 13% higher and
1 % lower, respectively.
The previous discussion on departures from Russell
Saunders coupling for Eu3+ is applicable to the excited
levels of Tb
3
+, with, of course, modifications caused by
the inversion of the levels of the multiplets and also
the increased values of the electrostatic and spin-orbit
parameters. An energy-level diagram is given in Fig. 2.
The energy levels and g values to 40 000 cm-
I
above
the ground state 7F6 are tabulated in Table IV, and
the eigenfunctions given in Table V. One immediate
difference between the Tb
3
+ energy-level scheme and
that of Eu3+ (for the excited levels below 40000 cm-
I
)
is that while the levels of Eu3+ form rather isolated
complex groups, for Tb3+ the levels have an almost
uniform distribution.
-0.2048 0.8336 0.0989
-0.0500 -0.0280
-0.0118 0.9208 0.1426 0.1851
-0.2473 0.8134 0.1432 0.2269 -0.0495
-0.1762 0.8400 0.1538 0.2184 0.0099
0.9046 0.2174 0.2276 -0.1323
0.9662 -0.1510
0.0030 0.0276 0.0071 0.1382 0.9241
0.0634 0.0411 0.0240 0.1468 0.9577
0.0660 0.0277 0.1748 0.9700
0.1511 0.9734
0.9669
C. 4/6 Configuration of Sm
H
The center of gravity of the 4J5Sd configuration of
Sm
H
lies about 20000 cm-
I
above that of the 4f6
configuration,r2 and the experimental data of Dieke
and SarupI3 indicate that the lower levels of tht 4J5Sd
configuration lie above the 5 DI level of the 4f6 con-
figuration. Therefore, data were available only for 5D
1
and lower levels, with the exception of 7F6 and 7F
s
,
which were not identified.
Although these data are rather limited, a calculation
was made which gave rather reasonable agreement
with the observed levels. The values obtained for the
12 G. H. Dieke, H. M. Crosswhite, and B. Dunn, J. Opt.Soc.
Am. 51, 820 (1961).
13 G. H. Dieke and R. Sarup, J. Chern. Phys. 36, 371 (1962).
Downloaded 30 Oct 2011 to 152.78.74.65. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions
2178 G. S. OFELT
TABLE VI. Energy levels of the 41
6
configuration of Srn2+ below
30000 ern-I.
Energy Energy
(ern-I)
g value Label
(ern-I)
g value Label
0 7FO 22408 1.195 6LlO
291 1.500 7FI 22 634 1.480 5D4
808 1.497 7F. 24 979 0.573 6H.
1 481 1.498 7F3 25 204 1.259 6H7
2 257 1,498 7F4 25 341 0.931 5H4
3099 1.497 7F6 25 360 1.141 6H6
3 981 1.496 7Fs 25 594 1.207 5H6
14 379 5Do 27 597 0.909 6/6
15 616 1.495
6D
I
27 781 0.668
6/
4
17 645 1.493 5D. 27 807 0.993
6F
2
19 997 1.488 6D, 27 877 1.229 6F3
20 106 0.723 5L6 27 963 0.041 6FI
20 776 0.916 5L7 28 254 1.298
6F
4
21 471 1.044 5LS 28 306
'Po
21 794 0.354 5Gt 28 531 1.238
5/
8
21 824 0.863
5G
3
28 605 1.086
5/
6
21 921 1.100
5G
4
28 631 1.183
5/
7
21 942 1.186
5G
5
28 647 1.183 5F5
22 059 1.131
5L
g 29 733 0.734 5K5
22 203 1.295
5G
6
parameters F2 and rare 330 and 1050 cm-I, which
are 18% and 20% lower than those for Eu3+.
Since the available data for Sm
2
+ are so few, it is
expected that the calculated energy-level scheme
would only be satisfactory for levels not too far above
5 D
I
Therefore, only the energy levels and g values to
30000 cm-
I
above the ground state 7 Fo are given in
Table VI. The eigenfunctions for the 7 F and 6 D mul ti-
plets are given in Table VII. An energy-level diagram
is given in Fig. 3. This diagram includes levels to
40000 cm-
I
to show the complexity of the energy-level
scheme above 30000 cm-
I

1lI. CRYSTAL-FIELD CALCULATIONS
The theory for calculation of the crystal-field split-
ting of the free-ion levels under the approximation of
the static model is now well known and has obtained
encouraging success in describing the rare-earth crystal-
field splitting. With the exception of the 7 F multiplet,
no satisfactory calculation of the Stark splitting of
the excited levels of either Eu3+ or Tb
s
+ has as yet
appeared in the literature. However, with the help of
the wavefunctions obtained from the free-ion calcula-
tions, some progress may be made in this area.
A. 7F Multiplet of EuCla and TbCI
s
7 F is the only state of maximum spin in the f6 and
f8 configurations. Since the crystal-field interaction is
diagonal in spin, and recalling that the TFJ levels of
both Eu3+ and Tb3+ are 94% or greater 7 F, a reason-
able approximation to the Stark splitting may be ob-
tained from a pure Russell-Saunders calculation. This
calculation has been made for Eu(C
2
H
6
S04)a9H20 by
Judd,14 which also includes correction factors of the
order of a few cm-
I
from a second-order perturbation
calculation, including the 6D composition of the wave-
function. In order to include J mixing for the 7 FJ
Stark splitting, the complete 7 Fe
Sk
crystal-field inter-
action matrices have been calculated,S and for EuCh
and TbCla the correction factors from the inclusion of
J mixing are found to be of the order of magnitude as
those from including the other states in the 7 FJ wave-
functions. The results of these calculations, including
both J mixing and the composition of the wavefunc-
tions, are presented in the following papers
7

11
where
comparison with the experimental data is made.
B. 6D Multiplet of EuCla and TbCta
When Stark splitting of the levels of the 6D multi-
plet is considered, the necessity to include the proper,
mixed, free-ion wavefunction in the calculation be-
40 X 1000 em'
... "
'0
'.
I.
'.

'0-
IK ~ - -
30
Sm III
I, ---;;- '1 ~ ~
'F I, IF
20
'0
'D
I, I,
'H
~ ~ ' H - 'H
.,
"
'L
...!!:---
.,
., -
~ - -
., --
o .,. ..!!,..---
o , '2 3 4 5 J I> 7
F 3300 .. -
1
t = 1'0 .. -
1
B 9 10 II 12
FIG. 3. Energy levels of Srn2+ below 40 000 ern-I.
14 B. R. Judd, Mol. Phys. 2, 407 (1959).
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i
6
CONFIGURATION OF RARE-EARTH IONS 2179
TABLE VII. Srn
H
7F and 6D eigenfunctions.
7F
6G
0.9704 0.0020 0.1597 -0.1751
0.9756 -0.0026 0.0095 0.1458 -0.1553 0.0388 -0.0050
0.9820 0.0005 0.0023 0.0121 0.1132 -0.1270 0.0372 0.0315
0.0166 -0.0169 0.0282
0.9684
-0.0883
-0.0033 0.0267 0.0987 -0.0794 0.0678 0.0775
-0.0261 -0.0467 0.0746 0.0010
0.9904
-0.0221
0.0120 0.0419 -0.0577 0.0725 0.0423
-0.0538 0.0573 0.0035 0.0051 -0.0003 -0.0002
0.9888
-0.0392
0.9837
-0.0652
-0.0819
-0.1161
0.0856 0.0070
0.1187 0.0088
0.0698 0.0380
0.0089 -0.0009 -0.0005 0.0001
0.0099 -0.0012 -0.0006 0.0002 -0.0001
5DO -0.2292 -0.1975 0.6939 -0.5429
-0.2023 0.0010 -0.2065 0.7193 -0.5589 -0.0520 -0.0362
-0.1575 0.0035 -0.0048 -0.2077 0.7477 -0.5750 -0.0803 -0.0765
-0.0157 0.0047 0.0067
-0.1057 -0.0093 -0.2049 0.7496 -0.5858 -0.1301 -0.0848
-0.0366 -0.0241 0.0183 0.0191 -0.0052
-0.0388
0.0223
-0.1755 0.7427 -0.5795 -0.1638 -0.0968
0.0751 -0.0761 -0.0580 -0.0559 0.0934 0.0230
See Table III for classification of states.
comes apparent even though the states are of the
order of 80% or more 5D. The free-ion wavefunctions
for the 5DJ levels contain a linear combination of the
three WU5D states, with small admixtures of 7F and
other quintet states, and small admixtures of triplet
states. For the lowest-lying D multiplet, the particular
linear combination of the three WUoD states is such
that, for both EuCh and TbCh, calculation of the
crystal-field splitting using only the WU5D composi-
tion of the DJ wavefunction produces a small over-all
extent of the splitting. This extent is of the order of
the experimentally obtained extent of the splitting,
but the calculated order of the Stark components does
not at all agree with the data. The experimental data
show the J.l=3 splitting of 5D3 and 5D4 is comparable
to the over-all DJ splitting. Since the crystal-field
matrix elements (WUoDI II U
6
1IW'U'5DI') are iden-
tically zero, other aLS states in the wavefunction
must be included in the calculation in order to produce
any splitting of these levels. If only the 7 F composition
is included, the splitting is still not sufficient, but re-
calling that the matrix elements of the unit tensor
U6 between 5 D states and quintet states with 4::;; L::;; 8
are, in general, nonzero, the quintet composition of
the wavefunction, although small, would have to be
included. Once this calculation has been performed,
reasonable agreement with the experimental data is
obtained. The results of these calculations are given
in the following papers.
7

11
Since these calculations are rather lengthy, it is
advantageous to define an "effective" singly reduced
matrix element of the unit tensor Uk:
(if;J II Uk II if;'J' )eff= La(aSLI)a(a' s' L' I')
A
X (jnaSLI II Ukllfka'S'L'I'),
where A represents the sets of quantum numbers
aSLa' S' L', and the a(aSLI) are the coefficients of
the state IraSLJ) occurring in the eigenfunction of
the eigenstate if;J of the free-ion problem, and these
coefficients may be taken as real. The matrix elements
WaSLI II Uk Ilra'S'L']') are the singly reduced
matrix elements, as usually defined in the literature.
Since calculation of these "effective" reduced matrix
elements becomes rather lengthy, they are most easily
evaluated by computer techniques. However, since
there are usually many terms in the summation, the
value of the "effective" reduced matrix element is a
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2180 G. S. OFELT
complicated function of the free-ion wavefunction's
composition.
C. Higher-Lying Levels
We, now, consider more highly excited levels than
the lower 5DJ levels. From inspection of Figs. 1 and 2,
it is easily seen that the crystal-field splitting of such
levels would require matrices of very large order,
because of the near degeneracy of the levels of the
various J manifolds. Also, the free-ion energy-level
positions may only be considered accurate to within
several hundred cm-
1
At this time an undertaking
of such a detailed calculation would be premature in
view of the complexities of the calculated Stark split-
tings for the 5DJ levels.
IV. CONCLUSIONS
The calculated free-ion energy-level scheme pre-
sented here should provide an aid for further experi-
mental analysis of the spectra of Eu
3
+, Tb*, and Sm*
ions. Most of the excited levels of these ions have
THE JOURNAL OF CHEMICAL PHYSICS
rather strong departures from Russell-Saunders cou-
pling, requiring lengthy intermediate coupling calcula-
tions for the Stark splitting in the crystal field. The
splitting obtained from such a calculation may be a
rather sensitive function of the free-ion wavefunction's
composition, and it seems that the information that
would be obtained would not warrant such lengthy
calculations, at least not until more experimental data
have been obtained. Another factor concerning the
advisability of the calculations for the excited levels
is that it seems necessary to include the configuration
interaction factor aLe L+ 1), for example, for the 5 L
multiplet, although the inclusion of this factor is not
reflected in the free-ion wavefunction as calculated
from the diagonalization of the electrostatic and spin-
orbit energy matrices.
ACKNOWLEDGMENT
The author is indebted to Professor G. H. Dieke for
his support and suggestions during the course of this
work.
VOLUME 38, NUMBER 9 1 MAY 1963
Energy Levels of Tb* in LaCl
3
and Other Chlorides*
K. S. THOMAS, S. SINGH, AND G. H. DIEKE
Johns Hopkins University, Baltimore, Maryland
(Received 14 December 1962)
The absorption and fluorescence spectra of Tb
a
+ in LaCb have been used to find the levels of Tba+, All
Stark components of 7F and 5D. were unambiguously established. The classification of the higher levels is
still doubtful.
The analysis was helped by Zeeman effects and particularly crystal field calculations. The latter gave
as crystal field parameters:
B
2
=92, Bl= -40, Bso= -30, B
6
6=290 cm-
l

Tba+ in YCk has a similar spectrum but, because of different crystal symmetry, with different fine struc-
ture. A third type of spectrum is obtained from pure TbCb.
1. INTRODUCTION
T
HE energy levels of the Tb
3
+ ion in crystalline salts
have been obtained in the past from the absorption
and fluorescence spectra. Gobrechtl interpreted the
structure of the fluorescence spectrum as transitions to
the 7 F ground multiplet of the Tb
H
ion, but as he
worked with only a dispersion of 500 A/rum, details
remained hidden. The only modern investigation of the
absorption spectrum of Tb
H
is that of Kahle and
Kalbfleisch,2 who dealt with parts of the absorption
spectrum of the ethyl sulfate.
* Work carried out with the partial support of the U. S. Atomic
Energy Commission.
1 H. Gobrecht, Ann. Phys. 28,673 (1937).
2 H. G. Kahle and H. Kalbfleisch, Z. Physik 166. 184 (1962).
In our laboratory a number of terbium salts were in-
vestigated, with regard to their Zeeman effects in ab-
sorption and fluoresecence, by S. Singh.
3
The present
paper deals in detail with the absorption and fluores-
cence spectrum of Tb
3
+ in hexagonal LaCl
a
, which, as
is now well known, has a number of favorable proper-
ties.
kt the past, the individual lines of the fluorescence
spectrum of some salts have given difficulties when an
attempt was made to determine the crystal field split-
tings, because they were not sharp enough, or there
were more lines than the theory allowed. No such diffi-
culties are present in the spectrum of Tb
3
+ in LaCIa, so
3 S. Singh, dissertation, Johns Hopkins University, 1957.
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