The first hyperpolarizability £], which is an important factor in the second-order nonlinear optical effect, of the 5-6-5 heterocyclic rigid-rod chromophores-based derivatives has been systematically investigated in this work, applying the first principle based software CASTEP and the semi-empirical software MOPAC There are four factors chosen for this computational analysis, including the effects of (i) various rigid-rod molecules, (ii) auxiliary ability of various five-member rings, (iii) donor ability, and (iv) conjugation length.
Results indicate that the benzobisimidazole (BBI)-based derivatives have larger £] values than those of benzobisthiazole (BBT) and benzobisoxazole (BBO)-based derivatives. The auxiliary donor ability of the pyrrole is larger than that of the thiophene and furan. In general, the £] value of various derivatives studied is parallel to the original donor strength and the trend in the donor is -N(CH3)2 > -NH2 > -OH > -CH3. In addition, the greater the conjugation length in the derivatives is, the higher the £] value. Further, from the analyses on the band-resolved £] values and the orbital density figures, it is found that the major contribution to the enhanced £] comes primarily from an efficient charge transfer from the donor side via the intermediate heterocyclic bridge to the acceptor side. Finally, a comparison between CASTEP and MOPAC reveals that CASTEP is more appropriate and accurate in predicting the optical properties of the heterocyclic-ring-based derivatives.
| Identifer | oai:union.ndltd.org:NSYSU/oai:NSYSU:etd-0110108-093918 |
| Date | 10 January 2008 |
| Creators | Mo, Hao-Jie |
| Contributors | Ming-Hsien Lee, Tzu-Chien Hsu, Jeh-Jeng Wang |
| Publisher | NSYSU |
| Source Sets | NSYSU Electronic Thesis and Dissertation Archive |
| Language | Cholon |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0110108-093918 |
| Rights | campus_withheld, Copyright information available at source archive |
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