Time-Dependent Approaches and Their Utility: Dynamical Formulations of Two-Dimensional Electronic Spectroscopy Signals and Electronic Structure Theory

We present time-dependent reframings of the theory of two-dimensional electronic spectroscopy signals and of electronic structure theory. The dynamical formulation of spectroscopic signals, in particular of two-dimensional wave-packet interferometry (WPI), is used to calculate and interpret signals from a spatially oriented energy transfer dimer. A general study of the detection of electronic energy transfer using WPI is carried out. The signals are interpreted using a semiclassical analysis that considers the paths taken by wave packets through phase space and the conditions required for their phase-space overlap. The dimer is also used to propose a WPI experiment capable of observing electronic intersite and interexciton coherence. Weak-coupling (intersite) and strong-coupling (interexciton) cases are studied, with a variety of systems differing in number of vibrational modes and in excited-state energies of the monomers. The time-dependent framing of electronic structure theory is a spectral filtering technique, where the Fourier transform of the time evolution of an antisymmetrized wave packet to the frequency domain reveals eigenstates and eigenenergies. Direct numerical integration of the time-dependent Schrödinger equation and semiclassical parametrizations are presented and compared as methods of obtaining the time evolution. The method is found to be accurate, and has some benefits; spectral filtering allows for many eigenstates to be obtained at once and includes electron correlation automatically. Future prospects for each of these works are discussed. This dissertation includes previously published and unpublished co-authored material.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Department of Chemistry and Biochemistry

Grantor dc:publisher

University of Oregon

Year dc:date.issued

2020

Author dc:creator

• Kiessling, Alexis

Advisor dc:contributor.advisor

• Cina, Jeffrey

• Electronic Structure Theory
• Fourier transform
• Ultrafast Spectroscopy
• Wave-packet dynamics
• Wave-packet Interferometry

Statement dc:rights

• All Rights Reserved.

Language dc:language.iso

en_US

Handle dc:identifier.uri

https://hdl.handle.net/1794/25680

OAI record oai:identifier

https://scholarsbank.uoregon.edu/server/oai/request?verb=GetRecord&metadataPrefix=dim&identifier=oai%3Ascholarsbank.uoregon.edu%3A1794%2F25680