Healy, David (1996) Solid solution studies of the molecular nonlinear optical properties of organic chromophores. Doctoral thesis, Durham University.
The work presented in this thesis describes an investigation into the properties and behaviour of nonlinear optical guest molecules doped into polymeric matrices. The interactions of the guest molecule 2-(N, N dimethylamino)-5-nitroacetanilide (DAN) with a polycarbonate and polymethyl methacrylate (PMMA) host are compared. A detailed characterisation of the two systems is described employing infra red spectroscopy and analysis of the chromophore alignment during electric field poling. The study reveals that hydrogen bond formation between the guest and the polar polycarbonate backbone accounts for the unusually good alignment stability previously reported in the polycarbonate system. The molecular hyperpolarisibility of DAN in PMMA is also measured and the apparent enhancement compared with solution measurements is accounted for by the more polar nature of the polymer environment. A new technique allowing the measurement of the dipole moment of polar molecules doped into thin polymer films is also presented. The technique is demonstrated on a series of zwitterionic chromophores whose measured dipole moments range from 30 to 40 D. Electrochroism measurements are performed to account for aggregation of the monomer species which then permits the first hyperpolarisibility of the molecules to be calculated. The values of dipole moment and hyperpolarisibility are found to be very sensitive to the choice of dielectric cavity shape used when deriving the local field correction factors. The measured values are therefore compared with theoretical calculations and a preferred cavity shape is proposed.
|Item Type:||Thesis (Doctoral)|
|Award:||Doctor of Philosophy|
|Copyright:||Copyright of this thesis is held by the author|
|Deposited On:||24 Oct 2012 15:12|