Third-order nonlinear optical properties of polymethine-based materials: a theoretical investigation

Gieseking, Rebecca Lynn

Title:

Third-order nonlinear optical properties of polymethine-based materials: a theoretical investigation

dc.contributor.advisor	Sherrill, C. David
dc.contributor.author	Gieseking, Rebecca Lynn
dc.contributor.committeeMember	Bredas, Jean-Luc
dc.contributor.committeeMember	Marder, Seth R.
dc.contributor.committeeMember	Perry, Joseph W.
dc.contributor.committeeMember	Kippelen, Bernard
dc.contributor.department	Chemistry and Biochemistry
dc.date.accessioned	2015-06-08T18:35:52Z
dc.date.available	2015-06-08T18:35:52Z
dc.date.created	2015-05
dc.date.issued	2015-04-07
dc.date.submitted	May 2015
dc.date.updated	2015-06-08T18:35:52Z
dc.description.abstract	Organic π-conjugated molecules and materials with large real parts and small imaginary parts of the third-order polarizability are of great interest for all-optical switching applications. In this dissertation, we use quantum-chemical and molecular-dynamics approaches to investigate the structure-property relationships that influence the nonlinear optical properties of π-conjugated molecules and materials. We begin with an overview of nonlinear optics, focusing in particular on the electronic properties of linear π-conjugated systems and some of the important problems that have limited device applications of these molecules to date. This is followed by a brief review of the computational methods employed in these studies. We then turn to the main results of the dissertation. Chapter 3 describes the structural dependence of the transition dipole moment between the first two polymethine excited states. Chapter 4 discusses the relationship between BLA, which depends on the geometric structure, and BOA, which probes electronic structure. Chapter 5 describes the benchmarking of computational methods to describe the symmetry-breaking of long polymethines and preliminary evidence regarding the role of vibrational modes in symmetry-breaking. Chapter 6 explains the negative third-order polarizability of tetraphenylphosphate and analogous systems. Chapter 7 focuses on molecular-dynamics studies of polymethine aggregation, particularly the relationships between chemical structure and the geometric and electronic structures of aggregates. Finally, Chapter 8 provides a synopsis of the work and discussion of further directions.
dc.description.degree	Ph.D.
dc.format.mimetype	application/pdf
dc.identifier.uri	http://hdl.handle.net/1853/53570
dc.language.iso	en_US
dc.publisher	Georgia Institute of Technology
dc.subject	Polymethines
dc.subject	Cyanines
dc.subject	Computational
dc.subject	Theoretical
dc.subject	Nonlinear optics
dc.subject	All-optical switching
dc.title	Third-order nonlinear optical properties of polymethine-based materials: a theoretical investigation
dc.type	Text
dc.type.genre	Dissertation
dspace.entity.type	Publication
local.contributor.advisor	Sherrill, C. David
local.contributor.corporatename	School of Chemistry and Biochemistry
local.contributor.corporatename	College of Sciences
relation.isAdvisorOfPublication	771cfa30-1ff7-4a12-b4c7-4f8e93b4860a
relation.isOrgUnitOfPublication	f1725b93-3ab8-4c47-a4c3-3596c03d6f1e
relation.isOrgUnitOfPublication	85042be6-2d68-4e07-b384-e1f908fae48a
thesis.degree.level	Doctoral