Spectra of ionized Zr, Nb, and Mo have been observed in sliding spark discharges at peak currents up to 4000 A on the 10.7 m normal and grazing incidence spectrographs at NBS. From these observations the group of 4s24p4–4s4p5 transitions in Zr vii, Nb viii, and Mo ix have been identified and measured. The energy parameters obtained from least-squares fits to the resultant energy levels are compared with Hartree-Fock calculations.
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Observed 4s24p4–4s4p5 transitions in the spectrum of Zr vii.
λ(Å)
Int.
σ(cm−1)
Classification
410.332
5
243 705.1
4s24p4 3P2–4s4p5
1P1
461.833
40
216 528.5
1D2–
1P1
495.100
50
201 979.4
3P2–
3P1
512.586
35
195 089.2
3P1–
3P0
518.638
100
192 812.7
3P2–
3P2
527.918
40
189 423.4
3P0–
3P1
530.700
35
188 430.4
3P1–
3P1
535.445
3
186 760.5
1S0–
1P1
557.835
70
179 264.5
3P1–
3P2
572.064
1
174 805.6
1D2–
3P1
603.736
30
165 635.3
1D2–
3P2
689.476
5
145 037.7
1S0–
3P1
TABLE II
Observed 4s24p4–4s4p5 transitions in the spectrum of Nb viii. Symbol: c, complex.
λ(Å)
Int.
σ(cm−1)
Classification
371.226
5
269 377.7
4s24p4 3P2–4s4p5
1P1
419.846
50
238 182.6
1D2–
1P1
446.944
50
223 741.7
3P2–
3P1
464.455
20
215 306.1
3P1–
3P0
470.055
100c
212 741.1
3P2–
3P2
478.055
20
209 181.0
3P0–
3P1
483.276
18
206 921.1
3P1–
3P1
488.023
3
204 908.4
1S0–
1P1
510.413
75c
195 919.8
3P1–
3P2
519.358
1
192 545.4
1D2–
3P2
550.832
30c
181 543.6
1D2–
3P2
627.846
5
159 274.7
1S0–
3P1
TABLE III
Observed 4s24p4–4s4p5 transitions in the spectrum of MO ix.
λ(Å)
Int.
σ(cm−1)
Classification
338.264
15
295 627.1
4s24p4 3P2–4s4p5
1P1
384.691
75
259 948.9
1D2–
1P1
406.319
50
246 112.0
3P2–
3P1
423.800
25
235 960.4
3P1–
3P0
428.959
100
233 122.5
3P2–
3P2
435.684
20
229 524.2
3P0–
3P1
443.388
18
225 536.1
3P1–
3P1
448.956
3
222 739.0
1S0–
1P1
470.484
40
212 547.1
3P1–
3P2
475.197
1
210 439.0
1D2–
3P1
506.462
30
197 448.2
1D2–
3P2
577.272
8
173 228.6
1S0–
3P1
TABLE IV
Energy levels in cm−1 of the 4s24p4 and 4s4p5 configurations of Zr vii, Nb viii, and Mo ix.
Config.
Term
J
Zr vii
Nb viii
Mo ix
4s24p4
3P
2
0.0
0.0
0.0
0
12 557.1
14 561.4
16 588.8
1
13 548.8
16 821.0
20 576.3
1D
2
27 175.9
31 196.7
35 674.5
1S
0
56 943.0
64 468.0
72 884.6
4s4p5
3P
2
192 812.2
212 740.6
233 122.9
1
201 980.5
223 742.4
246 113.0
0
208 638.0
232 127.1
256 536.7
1P
1
243 704.0
269 377.5
295 624.1
TABLE V
Energy parameters in cm−1 and mean errors Δ of least-squares fits for the 4s24p4 and 4s4p5 configurations of Zr vii, Nb viii, and MO ix. Value of Eav for the 4s24p4 configuration listed in the HF column is that obtained by diagonalizing the energy matrix with the HF parameters, 3P2 level set at zero.
Zr vii
Nb viii
Mo ix
Config.
Parameter
HF
Fitted
Fitted/HF
HF
Fitted
Fitted/HF
HF
Fitted
Fitted/HF
4s24p4
Eav
16 934
16 397 ± 22
19 340
19 025 ± 25
22 014
21 963 ± 26
F2(4p4p)
83 722
70 565 ± 160
0.843
89 093
75 514 ± 188
0.848
94 331
80 369 ± 204
0.852
ζ4p
10 039
11 076 ± 44
1.103
12 278
13 554 ± 46
1.104
14 809
16 355 ± 44
1.104
α (4p4p)
−59 ± 12
−62 ± 13
−65 ± 14
Δ
45
49
51
4s4p5
Eav
222 691
209 146 ± 1
241 044
231 266 ± 5
261 622
253 947 ± 10
G1 (4p4s)
111 379
66 357 ± 4
0.59578
118 196
72 402 ± 18
0.6126
124 847
78 157 ± 33
0.6260
ζ4p
10 018
10 551 ± 2
1.0532
12 253
12 925 ± 9
1.0548
14 780
15 610 ± 16
1.056
Δ
2
10
18
TABLE VI
Calculated energy level values in cm−1 and percentage compositions for the 4s24p4 configurations of Zr vii, Nb viii, and Mo ix. Negative eigenvector components are preceded by a minus sign.
Atom
J
E(obs)
E(calc)
O − C
Percentage composition
Zr vii
0
12 557
12 596
−39
85% 3P − 15% 1S
56 943
56 937
6
85% 1S + 15% 3P
1
13 549
13 538
11
100% 3P
2
0
−19
19
91% 3P + 9% 1D
27 176
27 181
−5
91% 1D − 9% 3P
Nb viii
0
14 561
14 601
−40
82% 3P − 18% 1S
64 468
64 460
8
82% 1S + 18% 3P
1
16 821
16 814
7
100% 3P
2
0
−27
27
89% 3P + 11% 1D
31 197
31 200
−3
89% 1D − 11% 3P
Mo ix
0
16 589
16 627
−38
78% 3P − 22% 1S
72 885
72 873
12
78% 1S + 22% 3P
1
20 576
20 574
2
100% 3P
2
0
−32
32
88% 3P + 12% 1D
35 674
35 677
−3
88% 1D − 12% 3P
TABLE VII
Comparison of present level values with previous results.
Predicted wavelengths in Å of transitions within the 4s24p4 configurations of Zr vii, Nb viii, and Mo ix. Wavelengths below 2000 Å are in vacuum, those above 2000 Å are in air. The uncertainties correspond to an estimated uncertainty of ± 1.4 cm−1 in the calculated wavenumbers.
Transition
Zr vii
Nb viii
Mo ix
3P2–1S0
1756.14 ± 0.04
1551.16 ± 0.03
1372.03 ± 0.03
3P1–1S0
2303.75 ± 0.07
2098.10 ± 0.06
1911.74 ± 0.05
1D2–1S0
3358.44 ± 0.16
3004.71 ± 0.13
2686.64 ± 0.10
3P2–1D2
3678.68 ± 0.19
3204.54 ± 0.14
2802.29 ± 0.11
3P2–3P1
7378.7 ± 0.8
5943.3 ± 0.5
4858.6 ± 0.3
3P0–1D2
6838.6 ± 0.7
6009.6 ± 0.5
5238.1 ± 0.4
3P2–3P0
7961.4 ± 0.9
6865.6 ± 0.7
6026.5 ± 0.5
3P1–1D2
7336.3 ± 0.8
6954.3 ± 0.7
6621.5 ± 0.6
Tables (8)
TABLE I
Observed 4s24p4–4s4p5 transitions in the spectrum of Zr vii.
λ(Å)
Int.
σ(cm−1)
Classification
410.332
5
243 705.1
4s24p4 3P2–4s4p5
1P1
461.833
40
216 528.5
1D2–
1P1
495.100
50
201 979.4
3P2–
3P1
512.586
35
195 089.2
3P1–
3P0
518.638
100
192 812.7
3P2–
3P2
527.918
40
189 423.4
3P0–
3P1
530.700
35
188 430.4
3P1–
3P1
535.445
3
186 760.5
1S0–
1P1
557.835
70
179 264.5
3P1–
3P2
572.064
1
174 805.6
1D2–
3P1
603.736
30
165 635.3
1D2–
3P2
689.476
5
145 037.7
1S0–
3P1
TABLE II
Observed 4s24p4–4s4p5 transitions in the spectrum of Nb viii. Symbol: c, complex.
λ(Å)
Int.
σ(cm−1)
Classification
371.226
5
269 377.7
4s24p4 3P2–4s4p5
1P1
419.846
50
238 182.6
1D2–
1P1
446.944
50
223 741.7
3P2–
3P1
464.455
20
215 306.1
3P1–
3P0
470.055
100c
212 741.1
3P2–
3P2
478.055
20
209 181.0
3P0–
3P1
483.276
18
206 921.1
3P1–
3P1
488.023
3
204 908.4
1S0–
1P1
510.413
75c
195 919.8
3P1–
3P2
519.358
1
192 545.4
1D2–
3P2
550.832
30c
181 543.6
1D2–
3P2
627.846
5
159 274.7
1S0–
3P1
TABLE III
Observed 4s24p4–4s4p5 transitions in the spectrum of MO ix.
λ(Å)
Int.
σ(cm−1)
Classification
338.264
15
295 627.1
4s24p4 3P2–4s4p5
1P1
384.691
75
259 948.9
1D2–
1P1
406.319
50
246 112.0
3P2–
3P1
423.800
25
235 960.4
3P1–
3P0
428.959
100
233 122.5
3P2–
3P2
435.684
20
229 524.2
3P0–
3P1
443.388
18
225 536.1
3P1–
3P1
448.956
3
222 739.0
1S0–
1P1
470.484
40
212 547.1
3P1–
3P2
475.197
1
210 439.0
1D2–
3P1
506.462
30
197 448.2
1D2–
3P2
577.272
8
173 228.6
1S0–
3P1
TABLE IV
Energy levels in cm−1 of the 4s24p4 and 4s4p5 configurations of Zr vii, Nb viii, and Mo ix.
Config.
Term
J
Zr vii
Nb viii
Mo ix
4s24p4
3P
2
0.0
0.0
0.0
0
12 557.1
14 561.4
16 588.8
1
13 548.8
16 821.0
20 576.3
1D
2
27 175.9
31 196.7
35 674.5
1S
0
56 943.0
64 468.0
72 884.6
4s4p5
3P
2
192 812.2
212 740.6
233 122.9
1
201 980.5
223 742.4
246 113.0
0
208 638.0
232 127.1
256 536.7
1P
1
243 704.0
269 377.5
295 624.1
TABLE V
Energy parameters in cm−1 and mean errors Δ of least-squares fits for the 4s24p4 and 4s4p5 configurations of Zr vii, Nb viii, and MO ix. Value of Eav for the 4s24p4 configuration listed in the HF column is that obtained by diagonalizing the energy matrix with the HF parameters, 3P2 level set at zero.
Zr vii
Nb viii
Mo ix
Config.
Parameter
HF
Fitted
Fitted/HF
HF
Fitted
Fitted/HF
HF
Fitted
Fitted/HF
4s24p4
Eav
16 934
16 397 ± 22
19 340
19 025 ± 25
22 014
21 963 ± 26
F2(4p4p)
83 722
70 565 ± 160
0.843
89 093
75 514 ± 188
0.848
94 331
80 369 ± 204
0.852
ζ4p
10 039
11 076 ± 44
1.103
12 278
13 554 ± 46
1.104
14 809
16 355 ± 44
1.104
α (4p4p)
−59 ± 12
−62 ± 13
−65 ± 14
Δ
45
49
51
4s4p5
Eav
222 691
209 146 ± 1
241 044
231 266 ± 5
261 622
253 947 ± 10
G1 (4p4s)
111 379
66 357 ± 4
0.59578
118 196
72 402 ± 18
0.6126
124 847
78 157 ± 33
0.6260
ζ4p
10 018
10 551 ± 2
1.0532
12 253
12 925 ± 9
1.0548
14 780
15 610 ± 16
1.056
Δ
2
10
18
TABLE VI
Calculated energy level values in cm−1 and percentage compositions for the 4s24p4 configurations of Zr vii, Nb viii, and Mo ix. Negative eigenvector components are preceded by a minus sign.
Atom
J
E(obs)
E(calc)
O − C
Percentage composition
Zr vii
0
12 557
12 596
−39
85% 3P − 15% 1S
56 943
56 937
6
85% 1S + 15% 3P
1
13 549
13 538
11
100% 3P
2
0
−19
19
91% 3P + 9% 1D
27 176
27 181
−5
91% 1D − 9% 3P
Nb viii
0
14 561
14 601
−40
82% 3P − 18% 1S
64 468
64 460
8
82% 1S + 18% 3P
1
16 821
16 814
7
100% 3P
2
0
−27
27
89% 3P + 11% 1D
31 197
31 200
−3
89% 1D − 11% 3P
Mo ix
0
16 589
16 627
−38
78% 3P − 22% 1S
72 885
72 873
12
78% 1S + 22% 3P
1
20 576
20 574
2
100% 3P
2
0
−32
32
88% 3P + 12% 1D
35 674
35 677
−3
88% 1D − 12% 3P
TABLE VII
Comparison of present level values with previous results.
Predicted wavelengths in Å of transitions within the 4s24p4 configurations of Zr vii, Nb viii, and Mo ix. Wavelengths below 2000 Å are in vacuum, those above 2000 Å are in air. The uncertainties correspond to an estimated uncertainty of ± 1.4 cm−1 in the calculated wavenumbers.
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