Theoretical Studies Of Electronic Properties And Electronic Processes In Conjugated Molecules
Electronic Theses of Indian Institute of Science
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Title |
Theoretical Studies Of Electronic Properties And Electronic Processes In Conjugated Molecules
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Creator |
Mukhopadhyay, Sukrit
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Subject |
Molecules - Electronic Properties
Theoretical Chemistry Conjugated Molecules - Electronic Structure Organic Conjugated Molecules Electroluminescence Polyfluorene Films Dendrimers Donor-Acceptor (DA) Complexes Conjugated Molecules Donor-Acceptor Molecule Theoretical Chemistry |
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Description |
This thesis deals with theoretical studies of electronic properties of organic conjugated molecules. The first chapter introduces different classes of organic conjugated molecules which possess high hole mobility, large quadratic non-linear response and low band gap. In this chapter, we further describe different photo-physical processes and the basic principles of various opto-electronic devices. The second chapter provides an introduction to various many-body techniques, which are employed in studying ground and excited state properties of organic conjugated systems. First, we describe the Hartree-Fock theory and the Density Functional (DFT) method. These are followed by full Configuration-Interaction (CI) methods and various semi-empirical methods (CNDO, INDO and NDDO). The INDO method is used in subsequent chapters to obtain the ground and excited state properties of organic conjugated molecules. In addition, we describe the restricted CI (SCI and SDCI) and the Density Matrix Renormalization Group (DMRG) methods. The third chapter of this thesis deals with a time evolution study to ascertain the role of the triplet state in the green emission of the ethyl-hexyl substituted poly-fluorene (PF2/6) films. To understand this phenomenon, we have modeled various non-radiative processes like (i) Inter-System Crossing (ISC), (ii) electron-hole Recombination (e-hR) and (iii) Triplet Quenching (TQ). These studies conclusively prove the contribution of triplet states to the 500 nm EL peak. In chapter four, we describe the origin of the unusual EL in tri-p-tolylamine (TTA) based hole conductors. In order to model this phenomenon, we have performed SCI calculations on TTA, its radical ions and allied hole conductors (TAPC and TPD). These calculations indicate that the unusual EL is due to low-lying charge-transfer (CT) state, which is stabilized by charge-dipole and charge-induced-dipole interactions. In chapter five, we turn our attention to the calculation of ground and excited state properties of a class of donor-acceptor (DA) system using ab-initio DFT and INDO methods. In these systems, DFT calculations along with INDO-SCI calculation, show strong intramolecular charge transfer interaction between the D and the A units. We have further calculated various properties like permanent dipole moments, oscillator strengths, Stoke’s shifts in various solvents etc. In chapter six, we focus on studying linear and non-linear optical properties of first generation nitrogen based dendrimers, using DMRG method. A novel scheme which includes the weights of the dipole allowed states in the computation of the density matrix is developed to obtain accurate dipole allowed excited states as well as the linear and nonlinear optical responses. Chapter seven deals with non-linear optical properties of weak donor-acceptor (DA) complexes formed between methyl substituted phenylenes (donor) and Chloranil or DDQ (acceptors). We have calculated the ground and the low-lying excited states of these DA complexes using INDO-SDCI method. The first hyperpolarizability (β) response coefficients are calculated using the Correction Vector (CV) technique, which are further used to obtain macroscopic depolarization ratios. By comparing the theoretical results with experimental findings, it can be shown that the slipped parallel configuration with a slight twist is the most preferred geometry of these weak DA complexes in solution.
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Contributor |
Ramasesha, S
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Date |
2011-07-08T05:11:17Z
2011-07-08T05:11:17Z 2011-07-08 2010-05 |
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Type |
Thesis
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Identifier |
http://etd.iisc.ernet.in/handle/2005/1265
http://etd.ncsi.iisc.ernet.in/abstracts/1646/G23718-Abs.pdf |
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Language |
en_US
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Relation |
G23718
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