OCCURRENCE AND CHARACTERIZATION OF ANIONIC BONDINGS IN TRANSITION-METAL DICHALCOGENIDES

被引:70
作者
JOBIC, S
BREC, R
ROUXEL, J
机构
[1] Institut des Matériaux de Nantes, Laboratoire de Chimie des Solides
关键词
D O I
10.1016/0925-8388(92)90269-F
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
Transition metal dichalcogenides MX2 crystallize in either two-dimensional or three-dimensional (3D) structures. This originates from the competition between cationic d levels and anionic sp levels. The occurrence of a chalcogen pairing may be obtained through oxidation of a ternary phase: Li2FeS2 leads to a metastable new binary compound Fe3+S2-(S2)2-. Such an electronic situation may also be found within the 3D family, the IrX2 (X = S, Se) and RhSe2 compounds with quite elongated X-X bonds attributed to strong strains. IrTe2 Should confirm the structural type presented by sulphur and selenium derivatives. Its previously reported CdI2-like structure is in fact based on a polymeric network with multiple Te-Te bonds (Ir(n)3+ (Te-1.5)2n) as confirmed by integrated overlap population calculations. This polymeric modification is presented by several other MTe2 phases and explains the very low c/a value (1.38) of the hexagonal cell observed in this family. The polymerization phenomena must be generalized to most pyrite-like MTe2 with the noticeable exception of MnTe2. The layered binary Cr2/3square1/3Te2 is another example of tellurium polymeric bondings. Finally a classification of structures taking into account not only the dimensionality but also the polymerization degree of such materials is suggested. From many examples, it is shown that the polymerizing behaviour of the heavy chalcogen anion seems to be much more general than expected and should lead to many charge transfer studies.
引用
收藏
页码:253 / 283
页数:31
相关论文
共 48 条
[11]   CRYSTAL STRUCTURES OF WTE2 AND HIGH-TEMPERATURE MOTE2 [J].
BROWN, BE .
ACTA CRYSTALLOGRAPHICA, 1966, 20 :268-&
[12]   GEOMETRICAL AND ELECTRONIC LINKS AMONG THE STRUCTURES OF MX2 SOLIDS - STRUCTURAL ENUMERATION AND ELECTRONIC STABILITY OF PYRITE-LIKE SYSTEMS [J].
BURDETT, JK ;
MCLARNAN, TJ .
INORGANIC CHEMISTRY, 1982, 21 (03) :1119-1128
[13]  
CANADELL E, 1991, UNPUB J SOLID STATE
[14]   LI2FES2, A CATHODIC MATERIAL FOR LITHIUM SECONDARY BATTERY [J].
DUGAST, A ;
BREC, R ;
OUVRARD, G ;
ROUXEL, J .
SOLID STATE IONICS, 1981, 5 (OCT) :375-378
[15]   CHALCOGEN SUBSTITUTION IN THE TA4P4S29 TUNNEL STRUCTURE - SYNTHESIS AND STRUCTURE OF TAPS6SE [J].
EVAIN, M ;
QUEIGNEC, M ;
BREC, R ;
SOURISSEAU, C .
JOURNAL OF SOLID STATE CHEMISTRY, 1988, 75 (02) :413-431
[16]   TA4P4S29 - A NEW TUNNEL STRUCTURE WITH INSERTED POLYMERIC SULFUR [J].
EVAIN, M ;
QUEIGNEC, M ;
BREC, R ;
ROUXEL, J .
JOURNAL OF SOLID STATE CHEMISTRY, 1985, 56 (02) :148-157
[17]  
EVAIN M, 1986, THESIS U NANTES
[18]   THE ELECTRONIC-STRUCTURE OF PYRITES, PARTICULARLY CUS2 AND FE1-XCUXSE2 - AN XPS AND MOSSBAUER STUDY [J].
FOLMER, JCW ;
JELLINEK, F ;
CALIS, GHM .
JOURNAL OF SOLID STATE CHEMISTRY, 1988, 72 (01) :137-144
[19]   INFRARED STUDY OF LITHIUM INTERCALATED PHASES IN THE LIXFES2 SYSTEM (0-LESS-THAN-X-LESS-THAN-2) - CHARACTERIZATION OF A NEW IRON DISULFIDE [J].
GARD, P ;
SOURISSEAU, C ;
OUVRARD, G ;
BREC, R .
SOLID STATE IONICS, 1986, 20 (03) :231-238
[20]   THE SYSTEM IRIDIUM-TELLURIUM [J].
HOCKINGS, EF ;
WHITE, JG .
JOURNAL OF PHYSICAL CHEMISTRY, 1960, 64 (08) :1042-1045