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Spectroscopic properties of praseodymium perchlorates in alcohols and 2-halogeno derivatives of ethanol. Part III

 

作者: B.Keller,   J.Legendziewicz,  

 

期刊: Journal of Applied Spectroscopy  (Springer Available online 2007)
卷期: Volume 62, issue 4  

页码: 725-730

 

ISSN:0021-9037

 

年代: 2007

 

DOI:10.1007/BF02606522

 

出版商: Springer_US-Boston

 

数据来源: Springer

 

摘要:

1.The oscillator strength values of Pr(ClO4)3in 2-chloroderivatives of ethyl alcohol vs. solvent polarizability exhibit a different relation than that observed in neodymium perchlorate solutions.2.The energies of f-d transitions for the above series shift to higher energies, indicating the expected effects of changes in electron densities in oxygen atoms of the solvent molecules. On the other hand, a shift energy of3P0bands towards the IR can be caused by nephelauxetic effects and is not realized for the CCl3CH2OH solution. Moreover, the f-d transition of the Pr3+ion in the latter solution appears at drastically low energies. This may indicate a decrease in the C-N and M-L distance in this system.3.The strange results of f-f transition-intensity variation in the series CH2FCH2OH, CH2ClCH2OH, CH2BrCH2OH, CH2ICH2OH indicate the competition of three factors:a/changes in the composition of the immediate environment of the Pr3+ion;b/changes in the dimerization or polymerisation of the solvent molecules caused by hydrogen bonding, which leads to polarizability of solvent molecule changes [2];c/splitting of d-orbitals of low-laying configuration and their shifts caused by the nephelauxetic effect [9].4.A decrease in the temperature of the solution leads to an effect close to the pressure one: as a result, a significant increase in the intensity of the f-f transition is observed, which is caused by shortening of Me−O distanc

 

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