Electronic Structure Method Development for Excited-State Chemistry
2017-09
Loading...
View/Download File
Persistent link to this item
Statistics
View StatisticsJournal Title
Journal ISSN
Volume Title
Title
Electronic Structure Method Development for Excited-State Chemistry
Authors
Published Date
2017-09
Publisher
Type
Thesis or Dissertation
Abstract
The accurate modeling of photochemistry requires robust dynamics simulations on correct potential surfaces. A pragmatic approach is to first compute potential surfaces with an accurate electronic structure method, fit the surfaces to an analytic function, and then run dynamics using the fitted surfaces. This approach will be referred to as fitted dynamics. The focus of this work is on the electronic structure aspect of fitted dynamics. Specifically, I will discuss my work on benchmarking and method development of multiconfiguration pair-density functional theory (MC-PDFT) and diabatization method development. MC-PDFT is very similar to Kohn-Sham Density Functional Theory (KS-DFT); however, MC-PDFT uses a multiconfigurational (MC) wave function (WF) instead of a single Slater determinant (SD), the MC-PDFT energy is a functional of the den- sity and on-top pair density instead of only the density, and the MC-PDFT energy is computed via post-SCF instead of optimizing the molecular orbitals (MOs). Due to the MC nature of excited states, MC-PDFT is a promising alternative to KS-DFT for photochemistry. To check if MC-PDFT is useful for photochemistry, we first bench- marked it on vertical excitation energies of atoms and organic molecules. We found that MC-PDFT exhibits quantitative accuracy. We have also explored new theory developments, which may be of use for practical photochemistry applications. With regards to diabatization, the dipole-quadrupole (DQ) and dipole-quadrupole- electrostatic-potential (DQ ) diabatization schemes were developed. They diabatize using simple one-electron properties and the methods exhibit applicability to general systems.
Description
University of Minnesota Ph.D. dissertation. September 2017. Major: Chemical Physics. Advisors: Laura Gagliardi, Donald Truhlar. 1 computer file (PDF); xii, 98 pages.
Related to
Replaces
License
Collections
Series/Report Number
Funding information
Isbn identifier
Doi identifier
Previously Published Citation
Suggested citation
Hoyer, Chad. (2017). Electronic Structure Method Development for Excited-State Chemistry. Retrieved from the University Digital Conservancy, https://hdl.handle.net/11299/192672.
Content distributed via the University Digital Conservancy may be subject to additional license and use restrictions applied by the depositor. By using these files, users agree to the Terms of Use. Materials in the UDC may contain content that is disturbing and/or harmful. For more information, please see our statement on harmful content in digital repositories.