Infrared absorption spectra of zirconium rhodanide complexes

Kharitonov, Yu. Ya.; Rozanov, I. A.

doi:10.1007/bf00909523

Cited by 3 publications

(3 citation statements)

References 14 publications

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“…The tetramer peak at 1000 cm –1 , which corresponds to a weak shoulder in the 2DPS spectrum at ∼1100 cm –1 , arises from wagging in a bridging OH where the H is hydrogen-bonded. The structure near 1000 cm –1 in the IR spectra of various Zr compounds has sometimes been assigned to the stretching mode of the zirconyl (ZrO) group, but no such species exists in the present models. Other work, on aqueous solutions of [Zr 4 (OH) 8 (H 2 O) 16 ] 8+ , assigns a peak in the 1018–1024 cm –1 range to a mode involving H 2 O, but there is no H 2 O in the present tetramer model.…”

Section: Resultsmentioning

confidence: 79%

Computational Modeling of the Structure and Properties of Zr(OH)₄

2018

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Ab initio molecular dynamics (AIMD), based on density functional theory, has been used to develop and test a model for amorphous Zr(OH)4, which is of interest as an agent for the adsorption of toxic gases. Beginning with an idealized and highly ordered structure based on two-dimensional layers of polymeric Zr(OH)4, AIMD at 300 K and above yields an amorphous structure. Disordering is seen to occur concomitantly with a reaction between acidic bridging OH sites and basic terminal OH to produce H2O and Zr–O–Zr bridges. The modeling also shows that Zr(OH)4 can be maintained in an artificial ordered state either by a regular array of hydrogen bonds within layers or by interaction between layers. Radial distribution functions and distributions of hydrogen-bond parameters are calculated for both the ordered and the amorphous structures, and a comparison between the two sets of results provides insight regarding the nature of the amorphous state. Infrared and proton nuclear magnetic resonance spectra are computed for the amorphous model, and chemical properties are evaluated by examining the acidity of different types of OH groups and also the reactions with SO2 and CO2. In particular, various mechanisms leading to sulfite formation during exposure to SO2 are examined in some detail. In all cases, good agreement with experiment is found, which indicates that the model is a suitable basis for analyzing the adsorption properties of amorphous Zr(OH)4.

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Section: Resultsmentioning

confidence: 79%

Computational Modeling of the Structure and Properties of Zr(OH)₄

2018

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“…Strong narrow band at 948 may be Zr = O (31, 32) NCS bound through N (27,33) " All infrared absorption peaks reported in this and the remaining tables are in cm"1 and represent the assignment made by the authors of the indicated references.…”

Section: Group IVmentioning

confidence: 83%

“…All of the evidence so far derives from infrared studies which yield absorption bands for certain zirconium and hafnium compounds in the region expected for metal-oxygen multiple bonds. For example, for eacli of the thiocyanato complexes ZrO(NCS)2 • MNCS • 2I120 (M = pyH, Cs, K, NH4, and Rb), there appears a rather narrow, medium strength absorption bond in the range 913-927 cm-1, which is purported (27) to be due to the Zr-0 multiple bond. In the compounds KZr0F3-2H20, ZrOF2, Zr^FioOs, ZrF4-H»0, bands recorded at 833, 864, 877, and 956 cm-1, respectively, are assigned (16) to the zirconyl frequencies, while in the compounds Hf4F]202, HfOF2, Hf4Fi40, HfF4-II20, the bands recorded at 889, 894, 896, and 970 cm"1, respectively, are assigned (16) to the hafnyl frequencies.…”

Section: Group IVmentioning

confidence: 99%