Yu
Wang
,
Huiting
Ma
,
Meina
Liu
,
Xintong
Li
,
Jia
Wei
and
Zhenwen
Dai
*
Key Laboratory of Physics and Technology for Advanced Batteries (Ministry of Education), College of Physics, Jilin University, Changchun 130012, China. E-mail: dai@jlu.edu.cn
First published on 21st November 2023
The archival data recorded by the Fourier transform spectrometer at the USA National Solar Observatory (NSO) were used to investigate the hyperfine structure (HFS) for Tb I and Tb II levels. The magnetic dipole HFS constant A values for 45 levels of Tb I ranging from 285.5 to 34223.95 cm−1 and for seven levels of Tb II below 36602 cm−1 were determined. To our best knowledge, the HFS constants for 34 out of 45 levels in Tb I and for two out of seven levels in Tb II are reported for the first time. This study extended the total number of experimentally measured magnetic dipole HFS constants A to 415 for Tb I and 92 for Tb II.
Tb is one of the rare-earth elements with the atomic number 65. Tb has only one stable isotope in nature, 159Tb, with a nuclear spin quantum number I = 3/2. Its nuclear magnetic dipole moment is μI = 4.2754μN (ref. 6) and nuclear electric quadrupole moment is Q = 1.432 b.7
Magnetic dipole and electric quadrupole hyperfine interaction constants, A and B respectively, of Tb I and Tb II energy levels had been measured previously by many different experiments. Childs8–11 used the atomic beam magnetic resonance technique, laser induced fluorescence (LIF) spectroscopy and high-precision laser-radiofrequency double-resonance measurement to obtain the HFS constants for 27 levels of Tb I. By a Fabry-Perot spectrometer, Arnoult et al.12 and Dekker et al.13 measured the HFS constants for three levels of Tb I and five levels of Tb II, respectively. Kumar et al.14 measured the HFS constants A and B for six levels of Tb I by analyzing Doppler-limited high-resolution laser optogalvanic spectra. LIF spectroscopy in hollow cathode discharge (HCD) lamps was used by Furmann et al.,15–17 Stefanska et al.18,19 and Suski et al.20 to measure the HFS constants of 63 Tb I levels of even parity and 290 Tb I levels of odd parity. Fourier transform spectroscopy (FTS) method was used by Lawler et al.21 to determine the HFS constants A of 83 levels and the constants B of 42 levels for Tb II, nine of which were previously unknown. Stefanska et al.22 reported the constants for 12 levels of Tb II using LIF spectroscopy in HCD lamps. Besides experimental investigations, Stefanska et al.19,22 and Furmann et al.17 performed HFS analysis of some levels in the configuration systems 4f85d6s2 + 4f85d26s + 4f96s6p of Tb I and 4f95d of Tb II by semi-empirical calculations.
There are 598 known Tb I and 153 known Tb II levels compiled by the National Institute of Standards and Technology (NIST), USA.23 The HFS constants for 381 levels of Tb I and 90 levels of Tb II have been experimentally determined to date. The HFS constants of many energy levels of Tb I and Tb II are still unknown. In the present work, we measured previously unknown HFS constants for some Tb I and Tb II levels using FTS spectra.
Index | Archive folder and filename | Buffer gas | Current (mA) | Wavenumber range (cm−1) | Coadds |
---|---|---|---|---|---|
1 | FTS49/991130R0.003 | Ar | 17 | 7929–34998 | 9 |
2 | FTS49/991130R0.004 | Ar | 22 | 7929–34998 | 9 |
3 | FTS49/991130R0.005 | Ar | 28 | 0–34998 | 10 |
4 | FTS49/991130R0.006 | Ar | 28 | 0–34998 | 10 |
5 | FTS49/991130R0.007 | Ar | 28 | 0–34998 | 50 |
6 | FTS49/991130R0.008 | Ar | 28 | 0–34998 | 20 |
7 | FTS49/991130R0.009 | Ar | 28 | 0–34998 | 10 |
8 | FTS49/991201R0.010 | Ar | 28 | 0–34998 | 50 |
9 | FTS49/991201R0.011 | Ne | 24 | 0–34998 | 9 |
10 | FTS47/980701R0.008 | Ne | 25 | 7929–34998 | 8 |
11 | FTS47/980702R0.010 | Ar | 30 | 7929–34998 | 38 |
12 | FTS44/971220R0.004 | Ar | 24 | 7929–34998 | 4 |
13 | FTS44/971220R0.007 | Ar | 30 | 7929–34998 | 16 |
(1) |
(2) |
Relative intensities of hyperfine transitions are as follows
(3) |
ΔF = 0, ±1 (F = 0↔0 unallowed). | (4) |
We performed fitting analysis of the HFS of Tb I and Tb II spectra using our fitting program that can determine HFS constants based on the theory above-mentioned and the Levenberg–Marquardt (LM) fit method.28 The LM fit method has some advantages over some conventional methods such as the Gauss–Newton and the steepest descent methods, etc. in terms of efficiency, convergence, broad applicability and uncertainty estimation, which are necessary for fitting HFS spectral lines with complex structures of hyperfine transition. The following parameters can be fitted by this program: the A and B values of investigated level, the Doppler linewidth, the center of gravity of the spectral line related to the investigated level, and the natural linewidth of a hyperfine transition. In the fitting process, we fixed the HFS A and B constants of the combining levels and allowed those of the investigated level to vary. The Voigt profile was used to fit the hyperfine components. There is obvious instrumental ringing around many of the observed spectral lines we used, due to insufficient resolving power used in the acquisition of these spectra. A more accurate line profile for these FTS spectral lines is a convolution between the Voigt function and a sinc function.29,30 Therefore, our HFS analysis program uses this type of convolution to fit each hyperfine component.
If there are multiple spectral lines with good signal-to-noise ratios for one transition connecting an investigated level, we used all these lines for HFS analyses. The A value from each transition can be determined by
(5) |
(6) |
The fitting uncertainty of parameter ΔAf can be determined by
(7) |
(8) |
When a measured level has multiple transitions, the final HFS constant AMean of this level is a weighted average of the A values from all transitions, and the weight factor is the inverse of the squares of the uncertainty ΔA. Its uncertainty was evaluated by
(9) |
The resulting HFS constants of 45 Tb I levels are listed in Table 2 and those of seven Tb II levels are listed in Table 3 where the columns five to seven give the combining levels and their published experimental HFS constant values. The level information in the first three and fifth columns of Tables 2 and 3 was taken from the NIST database,23 where further original references by Martin et al.31 and Sansonetti et al.32 are cited. Columns four and eight show the number of transitions used for a studied level and the number of lines used for a transition, respectively. For the investigated levels with multiple transitions, the A and B values determined from each transition and their weighted mean AMean and BMean are all listed. The uncertainty estimates of most of the A and B constants are less than 3% and 7%, respectively. Altogether, 73 transitions were investigated which were specially selected with the aims to connect the combining levels whose HFS constants are known. They involve 182 spectral lines from different spectra and these lines have signal-to-noise ratios (SNRs) of above 20, 20–10 and 10–5 with the proportion of 41%, 35% and 24%, respectively. Some examples of typical experimental profiles together with the best fitted line profiles are shown in Fig. 1.
Investigated level | No. of transitions | Combining level | No. of lines | A constant (MHz) | B constant (MHz) | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Energy (cm−1) | Parity | J | Energy (cm−1) | A (MHz) | B (MHz) | This work | Previous | This work | Previous | ||||
A | A Mean | B | B Mean | ||||||||||
a Stefanska et al.18 b Childs et al.9 c Furmann et al.17 d Arnoult et al.12 e Childs et al.10 f Furmann et al.16 g Kumar et al.14 h Furmann et al.15 i Stefanska et al.19 j Suski et al.20 | |||||||||||||
285.500 | e | 13/2 | 2 | 21083.72 | 1091(2)a | 457(11)a | 3 | 532(4) | 531(3) | 532.204(2)b | 862(87) | 879(48) | 928.861(30)b |
24392.79 | 338.8(4)c | 660(6)c | 3 | 530(3) | 531(6)d | 886(57) | 989(60)d | ||||||
462.080 | e | 15/2 | 2 | 21812.08 | 688(3)c | 722(10)c | 3 | 473(4) | 473(1) | 472.643(2)b | 1207(79) | 1148(38) | 1154.239(17)b |
21837.92 | 885.7(4)e | 1300(5)e | 3 | 473(1) | 472.6 (4)e | 1130(44) | 1157(5)e | ||||||
471(6)d | 1169(60)d | ||||||||||||
509.845 | e | 11/2 | 2 | 18607.24 | 843.9(8)f | 863(4)f | 3 | 578(3) | 580(2) | 577.465(2)b | 941(68) | 1003(64) | 989.917(30)b |
19606.52 | 1017.4(2)a | 618(3)a | 3 | 582(2) | 571(10)g | 1053(61) | 962(20)g | ||||||
573(6)d | 1049(60)d | ||||||||||||
577.4(4)e | 995(5)e | ||||||||||||
2310.090 | e | 11/2 | 2 | 25724.41 | 552(2)a | 814(37)a | 3 | 400(4) | 403(4) | 405.106(3)b | −92.638(50)b | ||
26787.51 | 949(3)f | 803(36)f | 3 | 408(5) | 405.1(4)e | −90(5)e | |||||||
4646.830 | e | 17/2 | 3 | 19131.45 | 906(2)f | 1412 (25)f | 2 | 481(5) | 483(3) | 481.738(2)b | 2347(168) | 2299(148) | 2245.914(50)b |
20534.69 | 926.0(1)a | 1392(2)a | 3 | 482(4) | 485(10)g | 2220(149) | 2232(20)g | ||||||
21837.92 | 885.7(4)e | 1300(5)e | 3 | 483(2) | 481.8(4)e | 2334(137) | 2250(5)e | ||||||
8506.710 | e | 17/2 | 3 | 28193.17 | 486(2)a | 1142(36)a | 3 | 906(5) | 909(5) | 915(5)h | 500(30)h | ||
30068.35 | 462.0(7)i | 1041(20)i | 2 | 908(4) | 915.3(5)i | 464(37)i | |||||||
30666.00 | 222(3)i | 389(24)i | 3 | 916(7) | |||||||||
13622.69 | o | 13/2 | 1 | 462.080 | 472.643(2)b | 1154.239(17)b | 3 | 355(4) | 510(92) | ||||
14888.11 | e | 15/2 | 2 | 0.000 | 673.753(2)b | 1449.330(40)b | 1 | 510(16) | 534(17) | ||||
28890.24 | 540.8(7)i | 638(14)i | 1 | 568(19) | |||||||||
14998.90 | o | 13/2 | 1 | 509.845 | 577.465(2)b | 989.917(30)b | 3 | 1061(7) | 413(119) | ||||
15189.23 | o | 11/2 | 2 | 285.500 | 532.204(2)b | 928.861(30)b | 2 | 1028(12) | 1040(12) | ||||
1371.045 | 602.3(5)e | 1271(5)e | 1 | 1054(13) | |||||||||
15825.17 | o | 9/2 | 1 | 509.845 | 577.465(2)b | 989.917(30)b | 3 | 930(11) | 1271(202) | ||||
16051.64 | o | 15/2 | 1 | 4646.830 | 481.738(2)b | 2245.914(50)b | 3 | 352(4) | 1729(100) | ||||
17441.07 | o | 13/2 | 1 | 2310.090 | 405.106(3)b | −92.638(50)b | 3 | 874(7) | |||||
17740.60 | o | 11/2 | 2 | 1371.045 | 602.3(5)e | 1271(5)e | 2 | 1106(26) | 1094(28) | ||||
8277.040 | 981(3)i | 820(24)i | 1 | 1137(62) | |||||||||
17932.42 | o | 17/2 | 1 | 8506.710 | 915(5)h | 500(30)h | 3 | 791(6) | 1008(83) | ||||
19080.13 | o | 15/2 | 1 | 285.500 | 532.204(2)b | 928.861(30)b | 3 | 1086.4(7) | 1087.0(3)j | 1616(22) | 1595(5)j | ||
19162.31 | o | 17/2 | 1 | 462.080 | 472.643(2)b | 1154.239(17)b | 3 | 736(9) | |||||
20928.12 | o | 13/2 | 2 | 509.845 | 577.465(2)b | 989.917(30)b | 2 | 853(4) | 893(5) | ||||
3719.705 | 354.454(3)b | 72.183(30)b | 1 | 1014(8) | |||||||||
21397.91 | o | 15/2 | 3 | 285.500 | 532.204(2)b | 928.861(30)b | 2 | 309(7) | 313(12) | ||||
462.080 | 472.643(2)b | 1154.239(17)b | 1 | 324(13) | |||||||||
5425.060 | 459.6(4)e | 1728(5)e | 2 | 312(12) | |||||||||
21946.46 | o | 21/2 | 1 | 12283.30 | 845.9(1)i | 1906 (11)i | 3 | 711(4) | 2980(207) | ||||
22278.93 | o | 11/2 | 1 | 509.845 | 577.465(2)b | 989.917(30)b | 3 | 1300.7(7) | |||||
22311.58 | o | 19/2 | 2 | 11879.20 | 757.6(4)i | 1167(24)i | 1 | 888(1) | 888(1) | ||||
12283.30 | 845.9(1)i | 1906(11)i | 2 | 914(67) | |||||||||
22524.15 | o | 11/2 | 1 | 509.845 | 577.465(2)b | 989.917(30)b | 2 | 760(2) | |||||
23031.84 | e | 15/2 | 1 | 0.000 | 673.753(2)b | 1449.330(40)b | 3 | 479(3) | 450(96) | ||||
23112.35 | e | 15/2 | 1 | 0.000 | 673.753(2)b | 1449.330(40)b | 3 | 395(5) | |||||
23191.65 | o | 9/2 | 1 | 2419.480 | 591.564(7)b | 733.233(70)b | 2 | 235(19) | |||||
23248.17 | o | 13/2 | 1 | 2310.090 | 405.106(3)b | −92.638(50)b | 2 | 107(6) | |||||
23438.36 | o | 11/2 | 1 | 509.845 | 577.465(2)b | 989.917(30)b | 3 | 361(2) | 929(33) | ||||
23519.94 | o | 9/2 | 1 | 509.845 | 577.465(2)b | 989.917(30)b | 2 | 887.1(6) | 229(6) | ||||
24824.89 | o | 13/2 | 2 | 285.500 | 532.204(2)b | 928.861(30)b | 2 | 269(7) | 280(7) | 726(183) | 750(182) | ||
462.080 | 472.643(2)b | 1154.239(17)b | 2 | 291(7) | 773(181) | ||||||||
24891.99 | o | 17/2 | 1 | 462.080 | 472.643(2)b | 1154.239(17)b | 3 | 242(2) | 1145(70) | ||||
25373.85 | e | 13/2 | 1 | 2771.675 | 682.911(3)b | 1167.489(50)b | 3 | 340(1) | 850(30) | ||||
25908.59 | o | 7/2 | 1 | 4695.505 | 215.653(15)b | −401.862(60)b | 3 | 485(3) | 491.0(3)j | 166(87)j | |||
27664.77 | o | 13/2 | 2 | 2310.090 | 405.106(3)b | −92.638(50)b | 2 | 586(12) | 586(9) | 592.8(4)j | 1161(284) | 1017(250) | 1014 (41)j |
3719.705 | 354.454(3)b | 72.183(30)b | 2 | 586(8) | 918(234) | ||||||||
27914.33 | o | 7/2 | 1 | 3174.575 | 652.766(20)b | 267.611(150)b | 2 | 815(13) | 821.5(2)j | 222(4)j | |||
28417.42 | o | 11/2 | 1 | 6351.750 | 439(2)i | 1122(29)i | 3 | 1004(6) | |||||
28585.93 | o | 5/2 | 1 | 4695.505 | 215.653(15)b | −401.862(60)b | 2 | 1164(42) | 1382(425) | ||||
29041.65 | o | 7/2 | 1 | 9145.230 | 1069(3)h | 1086(7)h | 3 | 761(3) | 715(26) | ||||
29861.37 | o | 11/2 | 1 | 5353.370 | 267(1)i | −449(10)i | 3 | 494(8) | |||||
30058.22 | o | 17/2 | 1 | 8506.710 | 915(5)h | 500(30)h | 3 | 755(7) | |||||
30253.95 | o | 5/2 | 1 | 7839.850 | 606.2(7)c | 429.7(4)c | 2 | 256(25) | |||||
30358.22 | o | 19/2 | 1 | 4646.830 | 481.8(4)e | 2250(5)e | 3 | 929(2) | 888.7(6)j | 2571(71) | −1240(16)j | ||
31093.42 | o | 7/2 | 1 | 6488.280 | 114.9(3)c | −498.7(7)c | 3 | 486(34) | |||||
33839.15 | o | 11/2 | 1 | 13071.30 | 703(4)i | −203(36)i | 3 | −251(11) | |||||
34223.95 | o | 21/2 | 1 | 12283.30 | 845.9(1)i | 1906(11)i | 2 | 309(7) |
Investigated level | No. of transitions | Combining level | No. of lines | A constant (MHz) | B constant (MHz) | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Energy (cm−1) | Parity | J | Energy (cm−1) | A (MHz) | B (MHz) | This work | Previous | This work | Previous | ||||
A | A Mean | B | B Mean | ||||||||||
a Lawler et al.21 b Dekker et al.13 c Stefanska et al.22 | |||||||||||||
0.000 | o | 8 | 3 | 25138.450 | 487(2)a | 1058(30)a | 3 | 1483(2) | 1483(2) | 1482(30)b | 1465(59) | 1438(71) | 1433(30)b |
25975.160 | 640(2)a | 1094(60)a | 2 | 1482(2) | 1453(90) | ||||||||
28488.810 | 664(3)c | 2054(25)c | 2 | 1483(3) | 1418(46) | ||||||||
1016.380 | o | 7 | 3 | 25138.450 | 485(3)c | 1014(64)c | 3 | −72(3) | −72(3) | −71(30)b | 1308(80) | 1323(81) | 1313(30)b |
25975.160 | 640(2)a | 1094(60)a | 3 | −72(3) | −72(6)c | 1343(83) | 1355(70)c | ||||||
28014.875 | 635.1(4)c | 1373(8)c | 3 | −72(3) | 1319(82) | ||||||||
25138.450 | e | 8 | 2 | 0.000 | 1482(30)b | 1433(30)b | 3 | 487(30) | 485(7) | 487(2)a | 1046(65) | 1056(70) | 1058(30)a |
1016.380 | −72(6)c | 1355(70)c | 3 | 485(7) | 485(3)c | 1074(85) | 1014(64)c | ||||||
27244.25 | e | 7 | 1 | 1016.380 | −72(6)c | 1355(70)c | 3 | 363(14) | |||||
28014.875 | e | 8 | 2 | 0.000 | 1482(30)b | 1433(30)b | 3 | 632(30) | 636(7) | 634(2)a | 1396(59) | 1392(63) | 1364(45)a |
1016.380 | −72(6)c | 1355(70)c | 3 | 636(7) | 635.1(4)c | 1380(112) | 1373(8)c | ||||||
28649.095 | e | 7 | 2 | 3010.050 | 1542(30)b | 1235(30)b | 3 | 745(30) | 743(5) | 745(3)a | 819(61) | 823(65) | 800(45)a |
3542.400 | −14(3)c | 947(74)c | 3 | 743(5) | 745(2)c | 840(113) | 775(24)c | ||||||
36602.00 | e | 8 | 1 | 13518.25 | 508(2)c | 1173(62)c | 2 | 364(8) |
In contrast to the hyperfine interaction of magnetic dipole, the electric quadrupole interaction has little effect on Tb HFS splitting. Since the resolution of the FTS spectra used in the present work is inadequate, we are unable to reliably determine the B constants of some levels. For these levels, regardless of whether B values are involved in the fits, there is almost the same conformity between the measured and fitted spectral lines. Therefore, their B constants were taken to be zero. However, for 21 Tb I levels and five Tb II levels, when B is zero the match between the fitted and experimental curves could not be achieved to a satisfactory degree. For example, Fig. 2 presents the comparison between the fitted curves with and without B constants of the 25138.450 cm−1 level in the fit for the transition to 0.00 cm−1 in Tb II. It is seen that when B was involved in the fit and its value is 1056(70) MHz, there is a significant improvement in conformance between the fitted and experimental curves. In this case, the B constants need to participate in parameter fits.
Fig. 2 Comparison of the fitted line profiles with (a) and without (b) B constant of the Tb II level 25138.450 cm−1 in the fit for the transition to 0.00 cm−1. The unit of B is MHz. |
The HFS constant results determined in the present work are in agreement with those previously published values in the literature, except for the A constant of two levels and the A and B constants of one level in Tb I. Our A constants for the two levels at 509.845 and 25908.59 cm−1 agree with the literature values within twice the uncertainties (2σ). The A constant 929(2) MHz of our work for the level at 30358.22 cm−1 was found by analyzing one transition observed in three spectra, a line at 25711.39 cm−1 for which the profiles in these spectra are almost the same, and this has a large difference compared with the A value of 888.7(6) MHz of Suski et al.20 Their B value −1240(16) MHz for this level has the opposite sign to our value of 2571(71) MHz. It should be noted that Suski et al.20 have analysed a different transition, a line at 19027.08 cm−1 with transition down to the level at 11331.14 cm−1 to determine HFS constants for the level at 30358.22 cm−1. Unfortunately, we were unable to observe this line. When we use the A and B values of Suski et al.20 for level 30358.22 cm−1 to simulate the line we observe in our spectra at 25711.39 cm−1 the resulting fit is rather poor compared to the fit with our HFS constants, as shown in Fig. 3. We suggest it would be prudent to check the HFS of this level in future work. The uncertainties in our A and B values are generally larger than those in the literature, which is due primarily to the limitations of relatively low SNR and resolution in the archival spectra that were used in our work.
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