Bringing to light the magic of photochemistry via AB initio nonadiabatic molecular dynamics
Abstract/Contents
- Abstract
- Controlling multistep chemical reactions triggered by internal conversion via a conical intersection is a challenging task that emphasizes limitations in theoretical and experimental techniques. Hypothesis-driven methodologies (e.g. characterization of critical points and biased molecular dynamics) are commonly employed to explore the chemical space and simulate reaction events. In this dissertation, I present a discovery-based, hypothesis-free computational approach based on first principles molecular dynamics to elucidate photochemical reaction pathways in organic chemistry. Using state-of-the-art graphical processing units-enabled electronic structure calculations we performed in total ~2ns of adiabatic and nonadiabatic ab initio molecular dynamics to describe the natural evolution of both the nuclear and electronic degrees of freedom that govern the interconversion between Donor-Acceptor Stenhouse Adducts' ground state intermediates. Additionally, we present direct and unambiguous observation of the ring-opening reaction path in 1,3-cyclohexadiene (CHD) and a-phellandrene (aPH) on the femtosecond timescale and sub-Ångström length scale by megaelectronvolt ultrafast electron diffraction and ab initio Multiple Spawning. We follow the carbon-carbon bond dissociation and the structural opening of the rings in CHD and aPH by direct measurement of time-dependent changes in the distribution of interatomic distances. Our work provides unprecedented and significant elements for the future design strategies of molecular photoswitches.
Description
| Type of resource | text |
|---|---|
| Form | electronic resource; remote; computer; online resource |
| Extent | 1 online resource. |
| Place | California |
| Place | [Stanford, California] |
| Publisher | [Stanford University] |
| Copyright date | 2021; ©2021 |
| Publication date | 2021; 2021 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Author | Sanchez, David Michael |
|---|---|
| Degree supervisor | Martinez, Todd J. (Todd Joseph), 1968- |
| Thesis advisor | Martinez, Todd J. (Todd Joseph), 1968- |
| Thesis advisor | Markland, Thomas E |
| Thesis advisor | Zare, Richard N |
| Degree committee member | Markland, Thomas E |
| Degree committee member | Zare, Richard N |
| Associated with | Stanford University, Department of Chemistry |
Subjects
| Genre | Theses |
|---|---|
| Genre | Text |
Bibliographic information
| Statement of responsibility | David Sanchez. |
|---|---|
| Note | Submitted to the Department of Chemistry. |
| Thesis | Thesis Ph.D. Stanford University 2021. |
| Location | https://purl.stanford.edu/dc260qb6358 |
Access conditions
- Copyright
- © 2021 by David Michael Sanchez
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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