Literature on MCD spectra of aqueous lanthanide perchlorate solutions is extensive (Antipovakarataeva et al., 1982; Go¨rller-Walrand, 1981; Go¨rller- Walrand and Beyens, 1980; Go¨rller-Walrand and Binnemans, 1998; Go¨rller- Walrand and Godemont, 1977a,b; Go¨rller-Walrand et al., 1979, 1980, 1982a, b; Kato and Nishioka, 1974; Kato et al., 1976; Pink, 1975; Sage et al., 1979).
On the other hand, a consistent set of absorption spectra for the lanthanides in aqueous HClO4 solution has been given (Carnall, 1979). The MCD spectra shown in Figure 27 provide useful complementary information to these previously reviewed absorption spectra for 10 trivalent Ln3þions and form to our knowledge the first complete set of MCD data throughout the lanthanide series in aqueous perchlorate solutions.
The solutions were prepared from the commercially available hydrated perchlorates by dissolving a known amount of salt in deminer- alized water. Concentrations were determined by titration following the Flaschka method (Carnall, 1979; Carnall et al., 1965, 1968). The absorption spectra were measured at room temperature on a Shimadzu spectropho- tometer (spectral bandwidth: 0.2 nm). All MCD spectra were recorded at room temperature on a Aviv 62 DS dichrometer (spectral bandwidth 0.1 nm (<7700 nm) and 0.2–0.4 nm (>700 nm), equipped with an electromag- net (Oxford Instruments) to provide a magnetic field of 1 tesla.
Tables 2–11 list all bands according to the classification of Carnall (1979). Peaks with molar absorptivitye<0.2 l mol1cm1are not listed unless they give rise to a MCD signal.
Energy (cm−1)
21,600 21,550 21,500 19,100 19,050 19,000 18,950 Energy (cm−1)
Arbitrary units
5D2 7F0 5D1 7F0
FIGURE 26 Simulated MCD spectra for the5D1,2 7F0transitions for Eu3þinC4v.
600 550 500 450 400 350
300 250
40,000 0 3 6 9
12 3P2
3P1 3P0
3H4
1D2 1I6
nm MCD
Δe/H (10−2 l mol−1 cm−1 tesla−1)
Energy (cm−1)
e (l mol−1 cm−1) Absorption
−15
−12
−9
−6
−3 0 3 6 9 12 15
Pr3+
35,000 30,000 25,000 20,000 15,000
600 550 500 450 400 350
300 250
40,000 0 2 4 6
2F7/22F5/2 2D5/2 2D3/2 4D7/2
4D1/2 4D5/2 4
D3/2
2D3/2 4G11/2 2P1/2
2G9/2 2K15/2
(2D,2F)3/2 4G9/2
4G7/2 2G7/2 4G5/2 2H11/2
4I9/2 nm MCD
Energy (cm−1) Absorption
−8.0
−6.4
−4.8
−3.2
−1.6 0.0 1.6 3.2 4.8 6.4 8.0
Nd3+
Δe/H (10−2 l mol−1 cm−1 tesla−1) e(l mol−1 cm−1)
35,000 30,000 25,000 20,000 15,000
700
10,000 15,0000
3 6 9 12
4F3/2
4F5/2
2H9/2
4S3/2
4F7/2
4F9/2
4I
9/2
nm MCD
Absorption
−25
−20
−15
−10
−5 0 5 10 15 20 25
Nd3+
Δe/H (10−2 l mol−1 cm−1 tesla−1)
Energy (cm−1) e (l mol−1 cm−1)
750 800 850 900 950
600 550 500 450 400 350
300
40,000 0.0 0.7 1.4 2.1 2.8
4H7/2 (4D,6P)5/2
4L15/2
6H5/2
4P5/2 4P3/24G5/2
4D7/2 4H9/2 4D3/2
6P7/2 4L13/2
(6P,4P)5/2 4G9/2
4I13/2 4M15/2 4G7/2
nm MCD
Absorption
−3.0
−2.4
−1.8
−1.2
−0.6 0.0 0.6 1.2 1.8 2.4 3.0
Sm3+
6P3/2
Energy (cm−1) Δe/H (10−2 l mol−1 cm−1 tesla−1)e (l mol−1 cm−1)
250
35,000 30,000 25,000 20,000 15,000
FIGURE 27 Continued
600 550 500 450 400 350
300 250
40,000 0.0 0.6 1.2 1.8 2.4
5G4
5K6 5F4
5H6
5H4
5G4,6 5G2
5D2
5L6 7
F0
5D1 5D4
(3K,3I)6
(5I,5H)6
nm MCD
Absorption
−1.2
−0.9
−0.6
−0.3 0.0 0.3 0.6 0.9
1.2 Eu3+
35,000 30,000 25,000 20,000 15,000
Energy (cm−1) Δe/H (10−1 l mol−1 cm−1 tesla−1)e (l mol−1 cm−1)
285 280
275
36,500 36,000 35,500
37,000 0.0 0.5 1.0 1.5 2.0
2.5 6I15/2
6I13/2 6I11/2
6I17/2 6I9/2
6I7/2
8S7/2 nm MCD
Energy (cm−1) Absorption
−15
−12
−9
−6
−3 0 3 6 9 12 15
Gd3+
Δe/H (10−2 l mol−1 cm−1 tesla−1)e (l mol−1 cm−1)
300
33,000 0.0
0.1 0.2 0.3 0.4
6P5/2 6P7/2
8S
7/2 nm MCD
Absorption
−5
−4
−3
−2
−1 0 1 2 3 4 5
Gd3+
32,500 32,000 31,500
305 310 315
Δe/H (10−3 l mol−1 cm−1 tesla−1)
Energy (cm−1) e (l mol−1 cm−1)
600 550 500 450 400 350
300 250
40,000 0.0 0.2 0.4 0.6 0.8
5K9 5I6
5I7 5I8
5H6 5H7
5D1
5L9 5L10 5G5
5G6 5D3
5D4
7F6 5L7,5L8
nm MCD
Absorption
−5
−4
−3
−2
−1 0 1 2 3 4 5
Tb3+
Δe/H (10−3 l mol−1 cm−1 tesla−1)
Energy (cm−1) e (l mol−1 cm−1)
35,000 30,000 25,000 20,000 15,000
FIGURE 27 Continued
600 550 500 450 400 350
300 250
15,000 20,000
25,000 30,000
35,000 40,000
0.0 0.6 1.2 1.8 2.4
(4P,4F)3/2 (4G,4P)5/2
(4G,4P)5/2
(4F,4D)5/2 (4P,4D)3/2
(4G,4H)7/2 4D7/2
6P3/2
6P7/2 4M19/2 4F7/2
4G11/2 4I15/2
4F9/2
6H15/2
4I13/2
4F3/2
4K17/2
nm MCD
Absorption
−6.0
−4.8
−3.6
−2.4
−1.2 0.0 1.2 2.4 3.6 4.8 6.0
Dy3+
Δe/H (10−2 l mol−1 cm−1 tesla−1)
Energy (cm−1) e (l mol−1 cm−1)
1000
15,000 0.0 0.6 1.2 1.8
2.4 6
F5/2
6H
15/2
6F3/2 nm
MCD
Absorption
−6.0
−4.8
−3.6
−2.4
−1.2 0.0 1.2 2.4 3.6 4.8 6.0
Dy3+
10,000 5000 2000
2000 3000 4000
Δe/H (10−2 l mol−1 cm−1 tesla−1)
Energy (cm−1) e (l mol−1 cm−1)
600 550 500 450 400 350
300 250
40,0000 1 2 3 4
5D3
(3H,5D,1G)4 (5G,5D,3G)4
(3F,3H,3G)4
(5G,3H)5 (5G,3G)5
3I7 3L8,3M10
nm MCD
Absorption
−10
−8
−6
−4
−2 0 2 4 6 8 10
Ho3+
35,000 30,000 25,000 20,000 15,000
Δe/H (10−2 l mol−1 cm−1 tesla−1)
Energy (cm−1) e (l mol−1 cm−1)
3K6
3L9,5G3 3K75G4
3H6 5G6
5F3
5F4 5I
8 5F5 5S2 5F2
3K8
200
50,0000 1 2 3 4
(3H,3G,3I)5 (3H,1I)6
(3F,5D)4
5I8
(3F,5D)3
5D2 nm MCD
Absorption
−10
−8
−6
−4
−2 0 2 4 6
8 Ho3+
Δe/H (10−2 l mol−1 cm−1 tesla−1)
Energy (cm−1) e (l mol−1 cm−1)
45,000 40,000
210 220 230 240
FIGURE 27 Continued
40,0000 2 4 6 8 4D7/2
2D5/2 2K13/2
4G9/2 4G11/2
4F3/2 4F5/24F7/2 2H11/2
4S3/2 4F9/2 4I15/2
2G7/2 4D7/2
(2H,2G)9/2
nm MCD
Absorption
−10
−8
−6
−4
−2 0 2 4 6 8 10
Er3+
35,000 30,000 25,000 20,000 15,000
Δe/H (10−2 l mol−1 cm−1 tesla−1)
Energy (cm−1) e (l mol−1 cm−1)
600 550 500 450 400 350
300 250
(2G,4F,2H)9/2
40,000 0.0 0.6 1.2 1.8 2.4
3P2 3P1
3P0 1D2
1G4
3H6
3F2 1I6
nm MCD
Absorption
−2.0
−1.6
−1.2
−0.8
−0.4 0.0 0.4 0.8 1.2 1.6 2.0
Tm3+
35,000 30,000 25,000 20,000 15,000
600 550 500 450 400 350
300 250
Δe/H (10−2 l mol−1 cm−1 tesla−1)
Energy (cm−1) e (l mol−1 cm−1)
In the tables, ymax=H and Demax=H¼ ð1=3298Þðymax=HÞ correspond to the difference between the extrema. Note that the values in the tables have to be multiplied by the factor that is given in the headings, so that, for example, for the 1D2 3H4 transition of Pr(ClO4)3) (Table 2) P¼3.08106,ymax=H¼1.65102mol1dl dm1tesla1 and Demax=H¼5:00102 l mol1cm1tesla1. Another example is the transition 5D1 7F0for Eu3þthat will be used in Section 8,5for the calculation of a MCD standard:
P¼1.62108,ymax=H¼40:3 mol1dl dm1tesla1andDemax=H
¼1:22102 l mol1cm1tesla1.
The sign of A terms or pseudo-A terms is given with respect to the previous conventions (Section 2.2). When no A shape is found, only the sign of the MCD dispersion is given; (þ) and () correspond,
1000
15,000 0.0 0.6 1.2 1.8 2.4
nm MCD
−2.0
−1.6
−1.2
−0.8
−0.4 0.0 0.4 0.8 1.2 1.6 2.0
Tm3+
3F3
3H4
3H6
10,000 5000 2000
Δe/H (10−2 l mol−1 cm−1 tesla−1)
Energy (cm−1) e (l mol−1 cm−1)
2000 3000
FIGURE 27 MCD and absorption spectra of rare-earth perchlorates in aqueous solution.
5 Note that a population factor of 65% for7F0and 35% for7F1is taken into account.
Transition n(cm1) l(A˚ ) 106P Mechanism
SignA term
emax
(l mol1cm1)
(mol1dl dm1tesla1)
(l mol1 cm1tesla1)
1D2 3H4 16,840 5938 3.08 ED þ 1.75 1.65 0.500
3P0 3H4 20,750 4819 2.54 ED 4.26 5.72 1.733
3P1,1I6 3H4 21,300 4695 7.63 ED 4.59 1.15 0.348
3P2 3H4 22,520 4440 15.06 ED þ 10.25 12.01 3.639
Transition n(cm1) l(A˚ ) 106P Mechanism SignAterm emax
(l mol1cm1)
(mol1dl dm1tesla1)
(l mol1cm1 tesla1)
4F5/2 4I9/2 12,480 8012
8.84 ED þ 5.78 3.45 1.045
2H9/2 4I9/2 12,590 7942
EDþMD þ 11.20 28.87 8.748
4F7/2 4I9/2 13,500 7407 8.90 EDþMD þ 6.64 8.61 2.609
4S3/2 4I9/2 13,500 7407
ED 5.29 6.40 1.939
4F9/2 4I9/2 14,700 6803 0.65 EDþMD þ 0.43 0.66 0.200
2H11/2 4I9/2 15,870 6301 0.15 ED
4G5/2 4I9/2 17,300 5780
9.76 EDþhyp 6.34 4.79 1.452
2G7/2 4I9/2 17,300 5780
4G7/2 4I9/2 19,160 5219 EDþMD þ 4.12 5.98 1.812
2K13/2 4I9/2 19,550 5115 7.01 ED 1.50
4G9/2 4I9/2
EDþMD
2K15/2 4I9/2 21,000 4762
2.33
ED þ 0.60 0.86 0.261
2G9/2 4I9/2 21,300 4694 EDþMD 0.64 0.59 0.179
(2D,2F)3/2 4I9/2 21,300 4694 ED
4G11/2 4I9/2 21,650 4619 9>
>=
>>
; EDþMD þ 0.43
2P1/2 4I9/2 23,250 4301 0.41 ED 0.94 1.18 0.358
2D5/2 4I9/2 23,900 4184 0.09 ED þ
(2P,2D)3/2 4I9/2 26,300 3802 0.03 ED þ
4D3/2 4I9/2 28,300 3533
9.42
ED 4.74 1.92 0.582
4D5/2 4I9/2 28,500 3509 ED 2.21
4D1/2 4I9/2 28,850 3466 9=
; ED 3.44 1.18 0.358
4D7/2 4I9/2 30,500 3279 EDþMD 0.56
2D3/2 4I9/2 33,400 2994 ED 0.31
2D5/2 4I9/2 34,450 2903 ED þ 0.16
2F5/2 4I9/2 38,506 2597 ED 0.14
Transition n(cm1) l(A˚ ) 106P Mechanism
SignA term
(l
mol1cm1)
(mol1dl dm1tesla1)
(l mol1 cm1tesla1)
4G7/2 6H5/2 20,050 4987 0.52 EDþMD
4M15/2 6H5/2 20,800 4808 1.53 ED
4I11/2 6H5/2 21,100 4739 1.53 ED þ 0.55 0.395 0.120
4I13/2 6H5/2 21,600 4630 0.68 ED þ 0.50 0.639 0.194
4G9/2 6H5/2 22,700 4405 0.39 ED þ
(6P,4P)5/2 6H5/2 24,050 4158 EDþMD 0.41 0.300 0.091
4L13/2 6H5/2 24,570 4070 0.43 ED þ 0.54 0.396 0.120
6P3/2 6H5/2 24,950 4008 3.84 EDþMD 3.02 2.98 0.903
4L15/2 6H5/2 25,650 3899 0.42 ED þ 0.22 2.75 0.833
6P7/2 6H5/2 26,750 3738 1.06 EDþMD þ 0.59 0.245 0.074
4D3/2 6H5/2 27,700 3610 1.23 EDþMD 0.68 0.387 0.117
(4D,6P)5/2 6H5/2 27,700 3610 1.23 ED þ
4H7/2 6H5/2 28,250 3540 0.06 EDþMD
4H9/2 6H5/2
29,100 3436 0.80 EDþMD þ 0.44 0.288 0.087
4D7/2 6H5/2
4G5/2 6H5/2 30,200 3311 EDþMD þ
4P3/2 6H5/2 31,550 3169 EDþMD 0.28 0.095 0.029
4P5/2 6H5/2 32,800 3049 ED
Transition
n
(cm1) l(A˚ ) 108P Mechanism
SignA term
emax
(l mol1cm1)
(mol1dl dm1tesla1)
(l mol1cm1tesla1)
5D0 7F1 16,920 5910 7.47 MD þ
5D1 7F1 18,691 5350 2.49 ED
5D1 7F0 19,028 5255 1.62 MD þ 0.113 0.403 0.122
5D2 7F1 21,164 4725 0.90 MD
5D2 7F0 21,519 4647 2.29 EDþhyp 0.0500 0.123 0.0370
5D3 7F1 24,038 4160 8.94 ED
5D3 7F0 24,408 4097 ED
5L6 7F0 25,400 3937 214.98 ED þ 3.41 7.97 2.42
5L7 7F1 25,974 3850 ED þ 0.340
5G2 7F0 26,300 3802 ED 0.320
5G5 7F1 26,325 3799 ED þ
5G4 7F0 26,620 3756 ED þ 0.420 1.52 0.461
5D4 7F1 27,300 3663 11.82 ED
5D4 7F0 27,641 3614 20.60 ED 0.730 3.51 1.06
5H7 7F1 30,656 3262 46.51 ED
5H4 7F0 31,250 3200 ED
(continued)
Transition
n
(cm1) l(A˚ ) 108P Mechanism
SignA term
emax
(l mol1cm1)
10 ðymax=HÞ (mol1dl dm1tesla1)
10 ðDemax=HÞ (l mol1cm1tesla1)
5H5,6 7F1 31,200 3205 ED
5H6 7F0 31,520 3172 79.90 ED þ 1.20 3.90 1.18
5F3 7F1 32,800 3048 13.15 ED
5F2 7F0 33,190 3013 ED
5F4 7F1 33,280 3005 ED
5F4 7F0 33,590 2977 ED 1.30 4.70 1.42
5I4 7F1 33,590 2977 ED
(5I,5H)6 7F1 34,100 2932 ED
(5I,5H)6 7F0 35,050 2855 ED þ 0.590 1.87 0.567
5I7 7F1 35,050 2855 ED þ
5K5 7F1 35,925 2784 ED
5K5 7F0 36,205 2762 ED
5K6 7F1 37,100 2695 7.39 ED þ
5K6 7F0 37,440 2671 23.16 ED þ 0.560 1.73 0.524
5F7 7F1 38,060 2627 ED þ
5G23 7F1 38,640 2588 55.44 ED
(3I,3K)6 7F0 39,062 2560 12.19 ED þ 0.360 1.34 0.406
5G4 7F0 39,897 2507 ED 0.810 1.03 0.312
5G5 7F1 40,100 2494 ED
Transition n(cm1) l(A˚ ) 106P Mechanism
SignA term
emax
(l mol1cm1)
(mol1dl dm1tesla1)
(l mol1cm1tesla1)
6P7/2 8S7/2 32,196 3106 0.073 MDþhyp þ 0.14 0.162 0.049
6P5/2 8S7/2 32,722 3056 0.041 EDþMD þ
6I7/2 8S7/2 35,932 2783 0.121 ED þ 0.24 1.42 0.430
6I9/2 8S7/2 36,232 2760 0.845 EDþMD þ 0.74 3.13 0.950
6I17/2 8S7/2 36,337 2752 ED þ 1.80 8.06 2.442
6I11/2 8S7/2 36,536 2737
1.914 ED þ 1.12 6.47 1.961
6I13/2 8S7/2 36,576 2734
6I15/2 8S7/2 36,697 2725 þ 2.81 11.30 3.424
6D9/2 8S7/2 39,620 2524 0.078 EDþMD
Transition n(cm1) l(A˚ ) 106P Mechanism
SignA term
emax
(l mol1cm1)
(mol1dl dm1tesla1)
(l mol1 cm1tesla1)
5D4 7F6 20,500 4878 0.52 EDþhyp þ 0.029 0.37 0.112
5D3 7F6 26,268 3807
8.46
ED
5G6 7F6 26,500 3773 EDþMD 0.16
5L10 7F6 27,100 3690 9=
; ED þ 0.25 0.282 0.085
5G5 7F6 27,800 3597
7.46
EDþMD
5D2 7F6 27,800 3597 ED
5L9 7F6 28,400 3521 9=
; ED þ 0.22 0.188 0.057
5L8 7F6 29,300 3413
3.04 ED
5L7 7F6 29,450 3395
ED
5D1 7F6 30,650 3262 0.37 ED þ 0.023 0.074 0.022
5H7 7F6 31,600 3164 2.02 EDþMD
5H6 7F6 33,000 3030 1.20 EDþMD
5H5 7F6 33,900 2950 0.18 EDþMD
5I8 7F6 35,200 2840 5.05 ED 0.20
Transition n(cm1) l(A˚ ) 106P Mechanism
SignA term
emax
(l mol1cm1)
(mol1dl dm1tesla1)
101 ðDemax=HÞ (l mol1cm1tesla1)
6F5/2 6H15/2 12,395 8068 1.55 ED þ 1.76 4.72 1.427
6F3/2 6H15/2 13,250 7547 0.33 ED þ 0.31 1.07 0.324
4F9/2 6H15/2 21,100 4739 0.21 ED
4I15/2 6H15/2 22,100 4525 0.44 EDþMD þ 0.23 0.32 0.097
4G11/2 6H15/2 23,400 4273 0.16 ED
4F7/2 6H15/2 25,800 3876
2.38
ED 0.82 0.22 0.067
4I13/2 6H15/2 MD
4K17/2 6H15/2 26,400 3787 9=
; MD 0.22
4M19/2 6H15/2 27,400 3649
2.85
ED 1.94 3.12 0.945
(4P,4D)3/2 6H15/2 ED
6P5/2 6H15/2
9=
; ED þ
6P7/2 6H15/2 28,550 3503 4.36 ED 2.32 1.92 0.582
(4F,4D)5/2 6H15/2 29,600 3378 0.39 ED þ 0.30 0.52 0.158
6P3/2 6H15/2 30,803 3247 2.59 ED þ 1.63 3.72 1.127
4H13/2 6H15/2 33,500 2985
1.43
MD þ 0.17 0.47 0.142
4D7/2 6H15/2 33,900 2950 ED 0.58 0.85 0.258
4G9/2 6H15/2 (34,311) (2914) ED
4G11/2 6H15/2 34,900 2865 ED þ
4L17/2 6H15/2 34,900 2865 9>
>>
>=
>>
>>
; ED þ
(4G,4H)7/2 6H15/2 35,900 2785 0.05 ED
(4G,4P)5/2 6H15/2 36,550 2736 ED 0.17 0.19 0.058
4F3/2 6H15/2 37,900 2639 ED þ
(4G,4P)5/2 6H15/2 38,900 2570 ED 0.30 0.39 0.118
(4P,4F)3/2 6H15/2 39,100 2557 ED 0.63 1.47 0.445
(4F,2G)9/2 6H15/2 41,050 2436 ED
4I15/2 6H15/2 41,700 2398 EDþMD
Transition n(cm1) l(A˚ ) 106P Mechanism
SignA term
emax
(l mol1cm1)
(mol1dl dm1tesla1)
101 ðDemax=HÞ (l mol1cm1tesla1)
5F5 5I8 15,500 6452 3.76 ED þ 3.04 3.32 1.006
5S2 5I8 18,500 5405
5.23 ED þ 1.65 2.37 0.718
5F4 5I8 18,653 5361
ED þ 4.49 9.31 2.821
5F3 5I8 20,600 4854 1.78 ED þ 1.75 6.54 1.982
5F2 5I8 21,100 4739
1.43 ED þ 0.76 1.57 0.476
3K8 5I8 21,370 4679
EDþMD þ 0.76 1.28 0.388
5G6 5I8 22,100 4524 6.00 EDþhyp 3.59 4.03 1.221
(5G,3G)5 5I8 23,950 4175 3.14 ED 2.35 3.24 0.982
5G4 5I8 25,800 3876
1.03 ED þ 0.44 0.57 0.173
3K7 5I8 26,200 3817
EDþMD
3H6 5I8 27,700 3610
3.24 ED
(5G,3H)5 5I8 27,700 3610
ED 2.04 1.55 0.470
5G3 5I8 28,800 3472
0.83 ED
3L9 5I8 29,000 3448
EDþMD 0.51 0.82 0.248
(3F,3H,3G)4 5I8 30,000 3333
0.80 ED þ
3K6 5I8 30,012 3332
EDþhyp 0.78 0.86 0.261
5G2 5I8 30,900 3236 0.13 ED
3L8 5I8 34,200 2924
1.01 EDþMD 0.47
3M10 5I8 34,200 2924
ED
(5G,5D,3G)4 5I8 34,800 2874 2.72 ED 3.06 2.98 0.903
(3H,5D,1G)4 5I8 36,000 2777 2.59 ED 1.84 2.16 0.655
3I7 5I8 38,500 2597 EDþMD
5D3 5I8 40,000 2500 0.54 ED 0.36
(3F,5D)4 5I8 41,550 2406 2.54 ED 3.12
Transition n(cm1) l(A˚ ) 106P Mechanism
SignA term
emax
(l mol1cm1)
(mol1dl dm1tesla1)
(l mol1 cm1tesla1)
4I9/2 5I15/2 12,400 8064 0.29 ED 0.24 0.697 0.211
4F9/2 5I15/2 15,250 6557 2.25 ED þ 2.09 3.24 0.982
4S3/2 5I15/2 18,350 5449 0.66 ED þ 0.70 1.87 0.567
(2H,4G)11/2 5I15/2 19,150 5222 2.89 EDþhyp 3.44 5.88 1.782
4F7/2 5I15/2 20,450 4889 2.27 ED þ 2.07 6.35 1.924
4F5/2 5I15/2 22,100 4525
1.25 ED þ 0.88 2.97 0.900
4F3/2 5I15/2 22,500 4444
ED þ 0.41 1.00 0.303
(2G,4F,2H)9/2 5I15/2 24,500 4037 0.80 ED þ 0.67 1.83 0.555
4G11/2 5I15/2 26,400 3788 5.92 EDþhyp 7.36 12.92 3.915
4G9/2 5I15/2 27,400 3649 1.75 ED 2.21 3.46 1.048
2K15/2 5I15/2 27,933 3580
0.91 MD 0.37
2G7/2 5I15/2 28,000 3571
ED þ 0.93 2.63 0.797
(2P,2D,4F)3/2 5I15/2 31,600 3164 0.09 ED þ
2K13/2 5I15/2 33,200 3012 0.12 EDþMD
4G5/2 5I15/2 33,400 2994 ED
4G7/2 5I15/2 34,050 2937 0.21 ED
2D5/2 5I15/2 34,850 2869 0.14 ED þ 0.17 0.498 0.151
(2H,2G)9/2 5I15/2 36,550 2736 0.44 ED 0.32 0.31 0.094
4D7/2 5I15/2 39,200 2551 10.2 ED 8.08 7.74 2.345
2I11/2 5I15/2 41,150 2430 ED 0.83
2L17/2 5I15/2 41,650 2400 EDþMD 0.29
4D3/2 5I15/2 42,300 2364 ED
2I3/2 5I15/2 43,550 2296 EDþMD 0.56
Transition n(cm1) l(A˚ ) 106P Mechanism
SignA term
emax
(l mol1cm1)
(mol1dl dm1tesla1)
(l mol1 cm1tesla1)
3H4 3H6 12,700 7874 2.12 ED 0.91 0.83 0.252
3F3 3H6 14,500 6897 3.91 ED þ 2.38 1.38 0.418
3F2 3H6 15,100 6622
ED 0.26 0.40 0.121
1G4 3H6 21,350 4684 0.71 ED 0.43 0.45 0.136
1D2 3H6 28,000 3571 2.38 ED 0.70 0.36 0.109
1I6 3H6 34,900 2865
0.84 EDþMD
3P0 3H6 35,500 2817
ED þ 0.33 0.15 0.045
3P1 3H6 36,400 2747 0.56 ED 0.36
3P2 3H6 38,250 2614 3.28 ED 0.94 0.43 0.130
respectively, to a signal on the positive and negative side of the MCD scale (De¼eeþ). As explained in Section 4.5 the ratioðDemax=HÞ=emaxleads toA1/Dby the use of Eq. (230). This determines the magnetic moment of the involved states.
The importance of the sign of the MCD terms has to a great extent been explained in Section 5. Additionally MCD enables to distinguish two peaks that in absorption are poorly resolved by the presence of two consecutive peaks with opposite sign, see, for example, Dy3þwhere the
6P5/2 6H15/2at 364.5 nm and6P7/2 6H15/2at 350.3 nm show, respec- tively, a positive and negative MCD signal.