Abstract
The very large cation-anion environmental effects on second-order nonlinear optical response observed in self-assembled stilbazolium monolayer ion-exchange experiments are investigated theoretically using the ZINDO/SOS quantum chemical formalism. Ion pairs consisting of the 4'-(dimethylamino)-A-methyl-4-stilbazolium cation with chloride, iodide, and p-aminobenzenesulfonate counteranions in differing mutual orientations, are examined as models to relate calculated ion pair hyperpolarizabilities to anion-exchange-induced changes in macroscopic linear optical and nonlinear optical response. Calculated hyperpolarizabilities depend strongly on the relative cation-anion packing configuration. In accord with anion exchange experiments, enhancements of the second-order nonlinear optical response on passing from Cl- to I- and p-aminobenzenesulfonate can be related to likely displacement of the bulkier I- and p-aminobenzenesulfonate anions from more closely packed structural arrangements originally produced as a consequence of the self-assembly process.
Original language | English (US) |
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Pages (from-to) | 400-404 |
Number of pages | 5 |
Journal | Chemistry of Materials |
Volume | 7 |
Issue number | 2 |
DOIs | |
State | Published - Feb 1995 |
ASJC Scopus subject areas
- Chemistry(all)
- Chemical Engineering(all)
- Materials Chemistry