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How Do the Different Defect Structures and Element Substitutions Affect the Nonlinear Optical Properties of Lacunary Keggin Polyoxometalates? A DFT Study
Author(s) -
Guan Wei,
Yang GuoChun,
Yan LiKai,
Su ZhongMin
Publication year - 2006
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200600450
Subject(s) - lacunary function , polyoxometalate , chemistry , heteroatom , polarizability , crystallography , nonlinear optical , atom (system on chip) , keggin structure , hyperpolarizability , molecule , stereochemistry , ion , nonlinear system , organic chemistry , catalysis , physics , ring (chemistry) , mathematics , quantum mechanics , computer science , pure mathematics , embedded system
Systematic DFT calculations have been carried out on the lacunary α‐Keggin polyoxometalate derivatives [PW 11 O 39 ] 7– , [XW 9 O 34 ] n – (X = Al III , Si IV , Ge IV , P V , As V , and Sb V ), [XW 9 M 2 O 39 ] n – , and [XW 9 M 3 O 40 ] n – (X = P V and Si IV , M = Mo VI , V V , Nb V , and Ta V ) to investigate the geometric structure and element substitution effects on the molecular nonlinear optical response. Analysis of the computed static second‐order polarizability ( β 0 ) predicts that the molecular nonlinear optical activity of lacunary Keggin polyoxometalate derivatives can be modified by replacing the central heteroatom and the addenda metal atom. Substitution of the central Al atom or the addenda V atom causes significant enhancement in the molecular nonlinearity. Moreover, the β 0 values are substantially dependent on the defect structures. This class of inorganic complexes possesses remarkably large molecular optical nonlinearity, especially for the partial substitution complex [SiW 9 Nb 2 O 39 ] 10– ( IIIc ), which has a computed β 0 value of 2071.0 a.u. Thus, lacunary Keggin polyoxometalates could become excellent candidates in the field of second‐order NLO. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)