1968
DOI: 10.1063/1.1669895
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Electronic Energy Levels of the Trivalent Lanthanide Aquo Ions. III. Tb3+

Abstract: A total of 23 experimental “free-ion” energy levels of Tb3+ (aquo) have been fit with an rms deviation of 56 cm−1. The resulting parameters are: E1 = 6021.5, E2 = 29.030, E3 = 608.54, ζ4f = 1709.5, α = 20.131, β = − 370.21, and γ = 1255.9. The latter three parameters arise from including the effects of configuration interaction in the calculation. Assignments were based upon a correlation between calculated and observed band intensities at energies up to ≈40 000 cm−1.

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Cited by 585 publications
(371 citation statements)
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“…Interestingly, the ratio B/C ~ 4 is retained in our calculations for the heavier transition metal ions, but not in the experimental data (2.2 for Nb 3+ , 6.5 for Rh 3+ ). The experimental data for the lanthanide(III) ions is exhaustive in aqueous solution, [22][23][24][25] which makes the f n excellent standards for the calibration of theoretical calculations. Here again, the electron repulsion parameters calculated for the gas phase are larger than those obtained experimentally, but we observe a steady improvement along the series for all parameters (F 2 + 37% for Pr 3+ vs. +24% for Tm…”
Section: Resultsmentioning
confidence: 99%
“…Interestingly, the ratio B/C ~ 4 is retained in our calculations for the heavier transition metal ions, but not in the experimental data (2.2 for Nb 3+ , 6.5 for Rh 3+ ). The experimental data for the lanthanide(III) ions is exhaustive in aqueous solution, [22][23][24][25] which makes the f n excellent standards for the calibration of theoretical calculations. Here again, the electron repulsion parameters calculated for the gas phase are larger than those obtained experimentally, but we observe a steady improvement along the series for all parameters (F 2 + 37% for Pr 3+ vs. +24% for Tm…”
Section: Resultsmentioning
confidence: 99%
“…37,38 This is because lanthanide f f f transitions are generally forbidden by both spin and Laporte selection rules. 39,40 In contrast, with cerium(III), the lowest energy electronic band in absorption corresponds to the allowed 4f f 5d transition. Although this results in a much broader band than with the other trivalent lanthanides, it does mean that the transition has a reasonable molar absorption coefficient.…”
Section: Introductionmentioning
confidence: 99%
“…where ∆E is the energy difference between the 4 I 15/2 and 4 F 9/2 energy levels (approximately 0.115 eV for aqua ions [43][44][45][46]), k B is Boltzmann's constant, and T is the temperature.…”
Section: Dymentioning
confidence: 99%