钠磷酸盐精细结构的拉曼光谱解析

doi:10.3964/j.issn.1000-0593(2009)07-1884-05

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Abstract Quantum chemistry ab initio calculation was applied to study the hyperfine structure of binary sodium phosphates. A series of phosphate model clusters were designed to simulate the microstructure of phosphates with different components. Closed-shell Hatree-Fock method (RHF) and the basis sets of 6-31G (d, p) were employed to optimize structures and calculate Raman frequencies of these phosphate model clusters. SIT (stress index of tetrahedron), which was well used in the study of silicate microstructures, had been adjusted before it was introduced to describe the microstructure of binary sodium phosphates. It was suggested that SIT of phosphates has good relationship with the Raman shift of the corresponding structures, which means SIT could also be used to study the hyperfine structure of binary sodium phosphates. Raman spectra of both solid and molten Na₅P₃O₁₀ were determined in the range of room temperature to 1 473 K. A phase transition between 873 and 1 073 K was observed, and the main peaks of Na₅P₃O₁₀ shifted to a lower frequency with increasing temperature. The microstructure units of Na₅P₃O₁₀ crystal are the types of Q²₁ and Q¹¹₂ with a ratio of 2∶1. With the increase in the temperature, various new microstructure units including Q₀, Q¹₁, Q²₁, Q¹¹₂, Q¹²₂ and Q²²₂ appeared while Na₅P₃O₁₀ was heated above the melting point, which led to the broadening and asymmetry of Raman spectra of molten Na₅P₃O₁₀. It came to an understanding that the microstructure units of phosphates may change at different temperature, especially above the melting points. The introduction of SIT and hyperfine structure could help analyze the Raman spectra of phosphates both qualitatively and quantitatively.

Key words：Phosphorus-oxygen tetrahedron;Melt;Quantum chemistry ab initio;Stress Index of Tetrahedron

Received: 2008-03-06 Accepted: 2008-06-09

ZTFLH:

O614.43

Corresponding Authors: YOU Jing-lin E-mail: jlyou@staff.shu.edu.cn

Cite this article:

ZHAO Si-jie,YOU Jing-lin,CHEN Hui, et al. Hyperfine Structure Study of Binary Sodium Phosphates by Raman Spectroscopy [J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2009, 29(07): 1884-1888.

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https://www.gpxygpfx.com/EN/10.3964/j.issn.1000-0593(2009)07-1884-05 OR https://www.gpxygpfx.com/EN/Y2009/V29/I07/1884

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