Akdeniz Zehra, Madden Paul A
Department of Physics, Istanbul University, Istanbul, Turkey.
J Phys Chem B. 2006 Apr 6;110(13):6683-91. doi: 10.1021/jp060064h.
Theoretical Raman spectra of the melts of NaF/AlF3 mixtures have been obtained from computer simulations in order to examine how the Raman spectra reflect the coordination structure around the Al3+ ions. The Raman spectra, both polarized and depolarized, are calculated from a model for the dependence of the polarizability of the system on the ionic coordinates which was inspired by electronic structure calculations of the polarizabilities of ions in a condensed-phase environment. The shapes of the spectra and their evolution with composition in the mixtures conform remarkably well to those seen experimentally, and we discuss the relationship between the bands seen in the spectra and the vibrational modes of the AlFn(3-n) coordination complexes which are found in the melts. Finally, we calculate quantities which relate to the degree of cross-linking between these coordination complexes and their lifetimes.
为了研究拉曼光谱如何反映Al3+离子周围的配位结构，通过计算机模拟获得了NaF/AlF3混合物熔体的理论拉曼光谱。极化和去极化拉曼光谱是根据一个系统极化率与离子坐标依赖关系的模型计算得出的，该模型的灵感来源于凝聚相环境中离子极化率的电子结构计算。光谱的形状及其随混合物组成的变化与实验观察结果非常吻合，并且我们讨论了光谱中出现的谱带与熔体中AlFn(3-n)配位络合物的振动模式之间的关系。最后，我们计算了与这些配位络合物之间的交联程度及其寿命相关的量。
