Chemical Effects on the Kα/Kβ Intensity Ratios in Some Transition Elements

Abstract

Kα/Kβ intensity ratios of 54Cr formd by the decay of various 54Mn-labeled manganese compounds are compared with those of vanadium, chromium and manganese compounds excited with X-rays. In all cases the Kα/Kβ intensity ratios are found to depend on the chemical state of an X-ray emitting atom, decreaeasing in general with an increase in the oxidation number of the central metal ion.

Parametrization of Kβ′′ and Kβ2,5 X-ray contributions in Kβ spectra of 3d transition metal compounds

“…Fig. 4 shows that the data published by Jones and Urch, 53 Tamaki et al 12 and Best 50 agree much better with our data for compounds with larger M-O average bond lengths than those with short bond lengths. I S1 calculated with experimental relative intensities of Torres Deluigi et al 44 and Tirao et al 43 for chromium oxides, and those of Bergmann et al 37 for manganese oxides follow similar exponential trend with the M-O average bond lengths, although their absolute values are systematically larger or smaller than ours.…”

“…For example, Chang et al reported 11 Kb/Ka intensity ratio 0.1479 for V metal, 0.1389 for VN, 0.1563 for VC. For V 2 O 5 they reported 0.1517 AE 0.0004, while Tamaki et al 12 reported 0.130.…”

“…By varying f i (Z) and a i parameters introduced in eqn (1), we obtained optimal fits of scaled normalized intensities I S1 , I S2 , and summed I S3 , defined by eqn (2). All numerical values used for parametrization are presented in Table 2 12 JON for Jones and Urch, 53 BES for Best, 50 TIR for Tirao et al, 43 TOR for Torres Deluigi et al, 44 UR S for Ur si c et al, 51 BER for Bergmann et al, 37 MUK for Mukoyama et al, 21 ASA for Asada et al, 67 IIH for Iihara et al, 52 TSU for Tsutsumi et al, 9 and YAS for Yasuda and Kakiyama. 68 ODB stands for ''our database''.…”

Use of Κβ/Κα Intensity Ratios for the Study of Annealing Processes in 51Cr-doped Solids

“…One method of introducing inner-shell vacancies is by means of the electron capture (EC) nuclear decay process. This approach has permitted TAMAKI, OMORI and SHIO-KAWA [2][3][4] and LAZZARINI et al [5] to measure large differences in theKß/Ka ratio for several 51 Cr-containing compounds as well as for 5 'Cr-doped solids. SHIOKAWA and coworkers [2] have thus proposed measurement of the Kß/Ka ratio as an "in situ" method for studying annealing reactions of 51 Cr in potassium Chromate.…”

“…SHIOKAWA and coworkers [2] have thus proposed measurement of the Kß/Ka ratio as an "in situ" method for studying annealing reactions of 51 Cr in potassium Chromate. However, the Kß/Ka differences between 51 Cr(III) and 51 Cr(VI) containing samples, of particular interest for annealing studies where observation of the overall process 51 Cr(III) -*• S1 Cr(VI) is the principal objective, showed considerable scatter from one solid matrix to another, indicating surprisingly large matrix effects or, possibly, reflecting inadequate self-absorption corrections applied to the (relatively) thick samples used by these authors [2][3][4][5].…”