Raman spectra of ionic liquids:: A simulation study of LaCl3 and its mixtures with alkali chlorides

被引:67
作者
Glover, WJ
Madden, PA
机构
[1] Univ Oxford, Dept Chem, Oxford OX1 3QZ, England
[2] Univ Calif Berkeley, Coll Chem, Berkeley, CA 94720 USA
关键词
D O I
10.1063/1.1792574
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Theoretical Raman spectra of the elpasolite-structured crystal Cs2NaLaCl6 and of molten mixtures of LaCl6 with NaCl and CsCl have been obtained from computer simulations in order to examine how the Raman spectra reflect the coordination structure around the La3+ ions. This system is a model for many other trivalent metal halides and for examining how the network structure of the pure melts is broken down by the addition of alkali halides with different structure-breaking powers. The results suggest a way of reconciling the conclusions of Raman studies about the structures of the melts with those of neutron and x-ray-diffraction studies, which have already been examined with the same simulation methods. 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. Some results on the lifetimes of the coordination complexes responsible for the appearance of the discrete Raman bands are discussed. (C) 2004 American Institute of Physics.
引用
收藏
页码:7293 / 7303
页数:11
相关论文
共 35 条
[1]  
Berne B. J., 2000, DYNAMIC LIGHT SCATTE
[2]  
BROOKER MH, 1983, ADV MOLTEN SALT CHEM, V5, P27
[3]  
Buckingham A. D., 1967, ADV CHEM PHYS, V12, P107, DOI DOI 10.1002/9780470143582.CH2
[4]   A transferable representation of the induced multipoles in ionic crystals [J].
Domene, C ;
Fowler, PW ;
Wilson, M ;
Madden, PA .
MOLECULAR PHYSICS, 2002, 100 (24) :3847-3865
[5]   FLUCTUATING DIPOLES AND POLARIZABILITIES IN IONIC MATERIALS - CALCULATIONS ON LIF [J].
FOWLER, PW ;
MADDEN, PA .
PHYSICAL REVIEW B, 1985, 31 (08) :5443-5455
[6]  
FOWLER PW, 1984, PHYS REV B, V29, P1035, DOI 10.1103/PhysRevB.29.1035
[7]   IN-CRYSTAL IONIC POLARIZABILITIES DERIVED BY COMBINING EXPERIMENTAL AND ABINITIO RESULTS [J].
FOWLER, PW ;
PYPER, NC .
PROCEEDINGS OF THE ROYAL SOCIETY OF LONDON SERIES A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES, 1985, 398 (1815) :377-393
[8]  
FOWLER PW, 1984, PHYS REV B, V30, P6131, DOI 10.1103/PhysRevB.30.6131
[9]   Response to "Comment on a critique of the instantaneous normal mode (INM) approach to diffusion" [J. Chem. Phys, 109, 4693 (1998)] [J].
Gezelter, JD ;
Rabani, E ;
Berne, BJ .
JOURNAL OF CHEMICAL PHYSICS, 1998, 109 (11) :4695-4696
[10]   A unified description of MCl3 systems with a polarizable ion simulation model [J].
Hutchinson, F ;
Wilson, M ;
Madden, PA .
MOLECULAR PHYSICS, 2001, 99 (10) :811-824