+publisher:"University of Colorado" +contributor:("Joel Eaves")

University of Colorado

1. Nummy, Thomas J. Polarization Dependent Angle Resolved Photoemission Spectroscopy for the Determination of Intrinsic Material Symmetries.

Degree: PhD, 2018, University of Colorado

URL: https://scholar.colorado.edu/phys_gradetds/244

► In this thesis I investigate the utility of the polarization and angle dependence of the photoemission matrix element in angle resolved photoemission spectroscopy (ARPES).… (more)

Subjects/Keywords: polarization; angle resolved photoemission spectrosopy; topological phase transition; intrinsic material symmetries; electronic wave function; Materials Science and Engineering; Physics

Record Details Similar Records Cite « Share

❌

APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Nummy, T. J. (2018). Polarization Dependent Angle Resolved Photoemission Spectroscopy for the Determination of Intrinsic Material Symmetries. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/phys_gradetds/244

Chicago Manual of Style (16^th Edition):

Nummy, Thomas J. “Polarization Dependent Angle Resolved Photoemission Spectroscopy for the Determination of Intrinsic Material Symmetries.” 2018. Doctoral Dissertation, University of Colorado. Accessed April 11, 2021. https://scholar.colorado.edu/phys_gradetds/244.

MLA Handbook (7^th Edition):

Nummy, Thomas J. “Polarization Dependent Angle Resolved Photoemission Spectroscopy for the Determination of Intrinsic Material Symmetries.” 2018. Web. 11 Apr 2021.

Vancouver:

Nummy TJ. Polarization Dependent Angle Resolved Photoemission Spectroscopy for the Determination of Intrinsic Material Symmetries. [Internet] [Doctoral dissertation]. University of Colorado; 2018. [cited 2021 Apr 11]. Available from: https://scholar.colorado.edu/phys_gradetds/244.

Council of Science Editors:

Nummy TJ. Polarization Dependent Angle Resolved Photoemission Spectroscopy for the Determination of Intrinsic Material Symmetries. [Doctoral Dissertation]. University of Colorado; 2018. Available from: https://scholar.colorado.edu/phys_gradetds/244

University of Colorado

2. Perkins, Russell James. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.

Degree: PhD, 2018, University of Colorado

URL: https://scholar.colorado.edu/chem_gradetds/273

► Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key… (more)

▼ Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key reactions occur in heterogeneous aqueous systems, where interfacial effects are particularly important. Despite the importance of aqueous environments and the tremendous amount of work done to study them, there are aspects that require further explanation and remain controversial. I have performed experimental studies to help elucidate the fundamental characteristics of aqueous systems, while examining specific phenomena across several fields. The genetic disorder phenylketonuria (PKU) can result in increased levels of the aromatic amino acid phenylalanine in human serum. Much of my work has focused on the driving forces behind partitioning of aromatic small molecules, including phenylalanine, into air-water or membrane-water interfacial regions, and the consequences of partitioning on interfacial properties. Drastically different behaviors for structurally similar aromatic molecules are observed, differences that cannot be explained by hydrophobic effects. These observations can be explained, however, through the development of a more detailed picture of interactions and partitioning, including the formation of interfacial aggregates. For phenylalanine, this partitioning appears to result in drastic changes in membrane morphology and permeability. This is a likely molecular-level cause for the damage associated with the disease state of PKU. Aqueous systems are further complicated by the reactivity of water. It often serves not only the role of a solvent, but also a reactant, a product, and/or a catalyst. I explore this reactivity using an organic molecule with relevance to environmental chemistry, zymonic acid. Zymonic acid forms spontaneously from pyruvic acid, an important atmospheric species. While zymonic acid exists as a single species in solid form when dissolved in DMSO, once in aqueous solution it quickly reacts with water and equilibrates with at least four other forms. I studied the details and kinetics of these equilibria via time-dependent NMR. Several surprising mechanistic details were uncovered, including a direct enol to geminal diol conversion and base-catalyzed lactone ring formation. The consequences of zymonic acid’s behavior are investigated in the context of environmental and prebiotic chemistry. Advisors/Committee Members: Veronica Vaida, Joel Eaves, Amy Palmer, Loren Hough, Garret Miyake.

Subjects/Keywords: aqueous interfaces; aromatic aggregation; mechanistic organic chemistry; membrane biophysics; preboitic chemistry; surfactants; Organic Chemistry; Physical Chemistry

Record Details Similar Records Cite « Share

❌

APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Perkins, R. J. (2018). Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/273

Chicago Manual of Style (16^th Edition):

Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2018. Doctoral Dissertation, University of Colorado. Accessed April 11, 2021. https://scholar.colorado.edu/chem_gradetds/273.

MLA Handbook (7^th Edition):

Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2018. Web. 11 Apr 2021.

Vancouver:

Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Internet] [Doctoral dissertation]. University of Colorado; 2018. [cited 2021 Apr 11]. Available from: https://scholar.colorado.edu/chem_gradetds/273.

Council of Science Editors:

Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Doctoral Dissertation]. University of Colorado; 2018. Available from: https://scholar.colorado.edu/chem_gradetds/273

University of Colorado

3. Perkins, Russell James. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.

Degree: PhD, 2017, University of Colorado

URL: https://scholar.colorado.edu/chem_gradetds/219

► Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key… (more)

▼ Many important chemical reactions from all branches of chemistry occur with water as a solvent. Furthermore, in environmental chemistry, biochemistry, and synthetic chemistry, key reactions occur in heterogeneous aqueous systems, where interfacial effects are particularly important. Despite the importance of aqueous environments and the tremendous amount of work done to study them, there are aspects that require further explanation and remain controversial. I have performed experimental studies to help elucidate the fundamental characteristics of aqueous systems, while examining specific phenomena across several fields. The genetic disorder phenylketonuria (PKU) can result in increased levels of the aromatic amino acid phenylalanine in human serum. Much of my work has focused on the driving forces behind partitioning of aromatic small molecules, including phenylalanine, into air-water or membrane-water interfacial regions, and the consequences of partitioning on interfacial properties. Drastically different behaviors for structurally similar aromatic molecules are observed, differences that cannot be explained by hydrophobic effects. These observations can be explained, however, through the development of a more detailed picture of interactions and partitioning, including the formation of interfacial aggregates. For phenylalanine, this partitioning appears to result in drastic changes in membrane morphology and permeability. This is a likely molecular-level cause for the damage associated with the disease state of PKU. Aqueous systems are further complicated by the reactivity of water. It often serves not only the role of a solvent, but also a reactant, a product, and/or a catalyst. I explore this reactivity using an organic molecule with relevance to environmental chemistry, zymonic acid. Zymonic acid forms spontaneously from pyruvic acid, an important atmospheric species. While zymonic acid exists as a single species in solid form when dissolved in DMSO, once in aqueous solution it quickly reacts with water and equilibrates with at least four other forms. I studied the details and kinetics of these equilibria via time-dependent NMR. Several surprising mechanistic details were uncovered, including a direct enol to geminal diol conversion and base-catalyzed lactone ring formation. The consequences of zymonic acid’s behavior are investigated in the context of environmental and prebiotic chemistry. Advisors/Committee Members: Veronica Vaida, Joel Eaves, Amy Palmer, Loren Hough, Garret Miyake.

Subjects/Keywords: aqueous interfaces; aromatic aggregation; mechanistic organic chemistry; membrane biophysics; preboitic chemistry; surfactants; Physical Chemistry

Record Details Similar Records Cite « Share

❌

APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Perkins, R. J. (2017). Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/219

Chicago Manual of Style (16^th Edition):

Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2017. Doctoral Dissertation, University of Colorado. Accessed April 11, 2021. https://scholar.colorado.edu/chem_gradetds/219.

MLA Handbook (7^th Edition):

Perkins, Russell James. “Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions.” 2017. Web. 11 Apr 2021.

Vancouver:

Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Internet] [Doctoral dissertation]. University of Colorado; 2017. [cited 2021 Apr 11]. Available from: https://scholar.colorado.edu/chem_gradetds/219.

Council of Science Editors:

Perkins RJ. Beyond Hydrophobicity: Aqueous Interfaces, Interactions and Reactions. [Doctoral Dissertation]. University of Colorado; 2017. Available from: https://scholar.colorado.edu/chem_gradetds/219

University of Colorado

4. Wilker, Molly Bea. Charge Transfer Dynamics in Complexes of Light-Absorbing CdS Nanorods and Redox Catalysts.

Degree: PhD, Chemistry & Biochemistry, 2015, University of Colorado

URL: https://scholar.colorado.edu/chem_gradetds/154

► The use of photoexcited electrons and holes in semiconductor nanocrystals as reduction and oxidation reagents is an intriguing way of harvesting photon energy to… (more)

▼ The use of photoexcited electrons and holes in semiconductor nanocrystals as reduction and oxidation reagents is an intriguing way of harvesting photon energy to drive chemical reactions. This dissertation describes research efforts to understand the photoexcited charge transfer kinetics in complexes of colloidal CdS nanorods coupled with either a water oxidation or reduction catalyst. The first project focuses on the charge transfer interactions between photoexcited CdS nanorods and a mononuclear water oxidation catalyst derived from the [Ru(bpy)(tpy)Cl]⁺ parent structure. Upon excitation, hole transfer from CdS oxidizes the catalyst (Ru²⁺→Ru³⁺) on a 100 ps – 1 ns timescale. This is followed by a 10 – 100 ns electron transfer that reduces the Ru³⁺ center. The relatively slow electron transfer dynamics may provide opportunities for accumulation of the multiple holes at the catalyst, which is necessary for water oxidation. The second project details the electron transfer kinetics in complexes of CdS nanorods coupled with [FeFe]-hydrogenase, which catalyzes H⁺ reduction. These complexes photochemically produce H₂ with quantum yields of up to 20%. The kinetics of electron transfer from CdS nanorods to hydrogenase play a critical role in the overall photochemical reactivity, as the quantum efficiency of electron transfer defines the upper limit on the quantum yield of H₂ generation. For optimized complexes, the electron transfer rate constant and the electron relaxation rate constant in CdS nanorods are comparable, with values of ≈107 s⁻¹, resulting in a quantum efficiency of electron transfer of 42%. Insights from these time-resolved spectroscopic studies are used to discuss the intricate kinetic pathways involved in photochemical H₂ generation in photocatalytic complexes. Finally, experimental results from photodriven H₂ generation and measurements of nanocrystal excited state lifetimes when the length of the nanocrystal-surface ligand was varied provide a deeper understanding into the mechanism for electron transfer from photoexcited nanorods to hydrogenase. Advisors/Committee Members: Gordana Dukovic, Niels Damrauer, David Jonas, Joel Eaves, Paul King.

Subjects/Keywords: Biomimetic; Photoluminescence; Transient Absorption; Chemistry; Nanoscience and Nanotechnology; Physical Chemistry

Record Details Similar Records Cite « Share

❌

APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Wilker, M. B. (2015). Charge Transfer Dynamics in Complexes of Light-Absorbing CdS Nanorods and Redox Catalysts. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/154

Chicago Manual of Style (16^th Edition):

Wilker, Molly Bea. “Charge Transfer Dynamics in Complexes of Light-Absorbing CdS Nanorods and Redox Catalysts.” 2015. Doctoral Dissertation, University of Colorado. Accessed April 11, 2021. https://scholar.colorado.edu/chem_gradetds/154.

MLA Handbook (7^th Edition):

Wilker, Molly Bea. “Charge Transfer Dynamics in Complexes of Light-Absorbing CdS Nanorods and Redox Catalysts.” 2015. Web. 11 Apr 2021.

Vancouver:

Wilker MB. Charge Transfer Dynamics in Complexes of Light-Absorbing CdS Nanorods and Redox Catalysts. [Internet] [Doctoral dissertation]. University of Colorado; 2015. [cited 2021 Apr 11]. Available from: https://scholar.colorado.edu/chem_gradetds/154.

Council of Science Editors:

Wilker MB. Charge Transfer Dynamics in Complexes of Light-Absorbing CdS Nanorods and Redox Catalysts. [Doctoral Dissertation]. University of Colorado; 2015. Available from: https://scholar.colorado.edu/chem_gradetds/154

University of Colorado

5. Smith, Candice Ashley. Nanoscale Reagents for the Detection and Treatment of Tuberculosis in Resource Limited Regions.

Degree: PhD, Chemistry & Biochemistry, 2015, University of Colorado

URL: https://scholar.colorado.edu/chem_gradetds/173

► Tuberculosis (TB) remains the second deadliest infectious disease after HIV/AIDS. TB most stubbornly has been spreading in resource limited regions. People in these regions… (more)

Subjects/Keywords: SELEX; Sub-Saharan Africa; Middle East; developing countries; emerging infectious disease; Animal Sciences; Biochemistry; Chemistry

Record Details Similar Records Cite « Share

❌

APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Smith, C. A. (2015). Nanoscale Reagents for the Detection and Treatment of Tuberculosis in Resource Limited Regions. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/173

Chicago Manual of Style (16^th Edition):

Smith, Candice Ashley. “Nanoscale Reagents for the Detection and Treatment of Tuberculosis in Resource Limited Regions.” 2015. Doctoral Dissertation, University of Colorado. Accessed April 11, 2021. https://scholar.colorado.edu/chem_gradetds/173.

MLA Handbook (7^th Edition):

Smith, Candice Ashley. “Nanoscale Reagents for the Detection and Treatment of Tuberculosis in Resource Limited Regions.” 2015. Web. 11 Apr 2021.

Vancouver:

Smith CA. Nanoscale Reagents for the Detection and Treatment of Tuberculosis in Resource Limited Regions. [Internet] [Doctoral dissertation]. University of Colorado; 2015. [cited 2021 Apr 11]. Available from: https://scholar.colorado.edu/chem_gradetds/173.

Council of Science Editors:

Smith CA. Nanoscale Reagents for the Detection and Treatment of Tuberculosis in Resource Limited Regions. [Doctoral Dissertation]. University of Colorado; 2015. Available from: https://scholar.colorado.edu/chem_gradetds/173

University of Colorado

6. Zhou, Dingyu. Global Sensitivity and Stochastic Pathway Analysis of Chemical Mechanisms.

Degree: PhD, Chemistry & Biochemistry, 2012, University of Colorado

URL: https://scholar.colorado.edu/chem_gradetds/84

► The use of theoretical kinetic modeling provides an invaluable tool for the study of biofuel blend development and optimization. These models provide a way… (more)

▼ The use of theoretical kinetic modeling provides an invaluable tool for the study of biofuel blend development and optimization. These models provide a way to simulate complex combustion systems and extract information without the need for costly experimental procedures. Indeed, these models often allow one to treat extreme conditions, such as those found in combustion engines, where in situ experiment is not yet feasible. However, many combustion models have large uncertainties in their rate coefficients and many models have been optimized for just a few specific conditions. Therefore, systematic improvement of biofuel combustion models is often necessary. Since these models are quite large, for example the n-butanol combustion mechanism contains 1446 reactions and 243 species, a brute force improvement all rate constant parameters is practically impossible. My Ph.D. work involved applying a global sensitivity analysis (GSA) method to combustion models of biofuel components in order to identify and improve the rate constants within the mechanisms that had the largest effect on the target simulation result. Specifically, my main focus was the combustion of n-butanol. GSA revealed that a target simulation result, the ignition time delay, was quite sensitive to self-reaction of the hydroperoxy radical HO2+HO2->H2O2+O2. The empirical rate coefficient for this reaction had a large uncertainty; therefore, high level ab initio calculations and transition state theory were used to calculate a more accurate rate coefficient for this reaction. The second part of my Ph.D. study involved developing an efficient method for determining the pathways taken during a chemical process using a stochastic method that followed ¡§single atoms¡¨. This study was motivated with the intent of extending the GSA method to account not only for the sensitivity of simulation results to single reactions, but to entire chemical pathways. The method I developed extracts not only reaction flow within the chemical network, but specifies the probabilities of exact chemical pathways. Advisors/Committee Members: Rex T. Skodje, Robert Parson, Joel Eaves, Veronica Vaida, J. Will Medlin.

Subjects/Keywords: Global Sensitivity Analysis; Stochastic Pathway Analysis; Chemistry

Record Details Similar Records Cite « Share

❌

APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Zhou, D. (2012). Global Sensitivity and Stochastic Pathway Analysis of Chemical Mechanisms. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/84

Chicago Manual of Style (16^th Edition):

Zhou, Dingyu. “Global Sensitivity and Stochastic Pathway Analysis of Chemical Mechanisms.” 2012. Doctoral Dissertation, University of Colorado. Accessed April 11, 2021. https://scholar.colorado.edu/chem_gradetds/84.

MLA Handbook (7^th Edition):

Zhou, Dingyu. “Global Sensitivity and Stochastic Pathway Analysis of Chemical Mechanisms.” 2012. Web. 11 Apr 2021.

Vancouver:

Zhou D. Global Sensitivity and Stochastic Pathway Analysis of Chemical Mechanisms. [Internet] [Doctoral dissertation]. University of Colorado; 2012. [cited 2021 Apr 11]. Available from: https://scholar.colorado.edu/chem_gradetds/84.

Council of Science Editors:

Zhou D. Global Sensitivity and Stochastic Pathway Analysis of Chemical Mechanisms. [Doctoral Dissertation]. University of Colorado; 2012. Available from: https://scholar.colorado.edu/chem_gradetds/84

University of Colorado

7. Donohoo-Vallett, Paul John. Control of Photophysical Processes Through Nuclear Motions — Design and Characterization.

Degree: PhD, Chemistry & Biochemistry, 2013, University of Colorado

URL: https://scholar.colorado.edu/chem_gradetds/94

► In order to achieve third-generation solar devices, the basic photophysics of light-absorbing materials must be thoroughly understood. Herein, vibrational motions are explored as potential… (more)

▼ In order to achieve third-generation solar devices, the basic photophysics of light-absorbing materials must be thoroughly understood. Herein, vibrational motions are explored as potential methods by which excited-state dynamics can be controlled. In an effort to prevent charge-recombination, vibrationally activated photoinduced dissociative electron transfer (ET) of the type [Ru^II(A)_n(L–X)] ²⁺ + hν⟶ [Ru^III(A)_n(L–X)•^–]²+*⟶ [Ru^III (A)_n(L•)]³⁺ + X^– (L = polypyridine ligand; X = halogen; A = ancillary ligand) is explored computationally and experimentally. Density functional theory (DFT) calculations employed a thermochemical cycle to determine structural and electronic factors influencing ΔE_rxn. Intramolecular strain is shown to decrease ΔE_rxn and the formation of a contact ion pair (CIP) state is determined to be a favored product. Thus, parent complex [Ru(tpy)₂]²⁺ (1) (tpy = 2,2':6',2''-terpyridine) is compared with two compounds [Ru(6,6''-Br₂-tpy)(tpy)]²⁺ (2) and [Ru(6,6''-Br₂-tpy)₂]²⁺ (3), that incorporate interligand strain. The crystal structure of 3 is distorted due to strain as compared to 1. While electronic absorption in 2 and 3 is weakened relative to transitions in 1, a strong interligand charge transfer (CT) transition is observed. Ultrafast transient absorption spectroscopy revealed coherent vibrational dynamics in 3 and 2 that were assigned to Br motion. In spite of additional strain, the excited-state lifetime of 3 is ~6x longer than 2. Constrained-DFT calculations shows the strain-induced geometric distortions in 3 causes a nesting of excited state surfaces, extending excited-state lifetime. Kinetic evidence is presented for C–Br bond scission in 3 and formation of the predicted CIP. A secondary project explores singlet fission (SF) — a process where one photon produces two excited-states. DFT calculations are used to explore a series of bistetracene (BT) molecular dimers connected by norbonyl bridges that exhibit through-space and through-bond electronic coupling. Dimer orientation and separation is shown to significantly affect SF driving force, Davydov splitting, and the magnitude of matrix elements important to CT-mediated SF. It is determined that BT1-cis, a norbonyl bridged dimer connected at the 1,2 tetracene positions with both tetracenes extending in the same direction, is most favorable for SF due to an exoergic SF driving force (–119 meV) and increased magnitudes of Davydov splitting and ET matrix elements. Advisors/Committee Members: Niels H. Damrauer, David M. Jonas, Cortland G. Pierpont, Joel Eaves, Henry Kapteyn.

Subjects/Keywords: density functional theory; electron transfer; photophysics; singlet fission; Chemistry; Physical Chemistry

Record Details Similar Records Cite « Share

❌

APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Donohoo-Vallett, P. J. (2013). Control of Photophysical Processes Through Nuclear Motions — Design and Characterization. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/chem_gradetds/94

Chicago Manual of Style (16^th Edition):

Donohoo-Vallett, Paul John. “Control of Photophysical Processes Through Nuclear Motions — Design and Characterization.” 2013. Doctoral Dissertation, University of Colorado. Accessed April 11, 2021. https://scholar.colorado.edu/chem_gradetds/94.

MLA Handbook (7^th Edition):

Donohoo-Vallett, Paul John. “Control of Photophysical Processes Through Nuclear Motions — Design and Characterization.” 2013. Web. 11 Apr 2021.

Vancouver:

Donohoo-Vallett PJ. Control of Photophysical Processes Through Nuclear Motions — Design and Characterization. [Internet] [Doctoral dissertation]. University of Colorado; 2013. [cited 2021 Apr 11]. Available from: https://scholar.colorado.edu/chem_gradetds/94.

Council of Science Editors:

Donohoo-Vallett PJ. Control of Photophysical Processes Through Nuclear Motions — Design and Characterization. [Doctoral Dissertation]. University of Colorado; 2013. Available from: https://scholar.colorado.edu/chem_gradetds/94

University of Colorado

8. Grumstrup, Erik Martin. Elucidation of Ultrafast Photophysics with Optical Pulse Shaping.

Degree: PhD, Physics, 2011, University of Colorado

URL: https://scholar.colorado.edu/phys_gradetds/182

► Optical pulse shaping is an incisive tool of laser spectroscopy that allows the experimentalist extensive flexibility to manipulate the electric field of an excitation… (more)

▼ Optical pulse shaping is an incisive tool of laser spectroscopy that allows the experimentalist extensive flexibility to manipulate the electric field of an excitation laser pulse. In this thesis, four applications of optical pulse shaping are examined. In Chapter 2, a partially non-collinear implementation of two-dimensional electronic spectroscopy is demonstrated for the first time on rubidium vapor. The use of a pulse shaper in this context is advantageous as it significantly reduces the complexity of the experimental apparatus. Unfortunately, non-ideal pulse shaping due to pixelation effects in some pulse-shaping devices leads to spurious pulse generation when the spatial masks become highly modulated. To model the effects on recovered 2D spectra, the optical Bloch model is numerically propagated with an explicit inclusion of the electric field modified by pixelation effects. Finally, steps necessary to minimize distortions are outlined. Chapter 3 describes a series of experiments designed to study the mechanism of multiple exciton generation in semiconductor quantum dots through open and closed loop coherent control schemes. The data collected with open loop control methods indicate that the initially formed exciton relaxes on an ultrafast time scale (<20 fs) revealing the reason for a lack of controllability in adaptive, closed-loop optimizations. Chapter 4 of this thesis examines the process of singlet fission in tetracene thin films employing coherent control and ultrafast pulse shaping. Singlet fission is a promising avenue to achieving highly efficient third generation photovoltaic devices, and in this work, closed-loop control suggests that low-frequency nuclear motions play a mechanistic role in tetracene singlet fission. Finally, Chapter 5 examines a specific class of pulse shaping, sinusoidal spectral phase modulation, which is widely employed in the coherent control community as a route toward an intuitive probe into molecular dynamics. This work seeks to build a bridge between the fields of nonlinear spectroscopy and coherent control by describing the light-matter interactions characteristic of this type of pulse shaping using the tools of time-dependent perturbation theory. This description allows experimentalists to predict and test theories of coherent control simply and with little ambiguity, furthering the usefulness of coherent control as a spectroscopic tool. Advisors/Committee Members: Niels H. Damrauer, David M. Jonas, Margaret Murnane, Gordana Dukovic, Joel Eaves.

Subjects/Keywords: 2DE spectroscopy; coherent control; pulse shaping; Optics; Physical Chemistry

Record Details Similar Records Cite « Share

❌

APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Grumstrup, E. M. (2011). Elucidation of Ultrafast Photophysics with Optical Pulse Shaping. (Doctoral Dissertation). University of Colorado. Retrieved from https://scholar.colorado.edu/phys_gradetds/182

Chicago Manual of Style (16^th Edition):

Grumstrup, Erik Martin. “Elucidation of Ultrafast Photophysics with Optical Pulse Shaping.” 2011. Doctoral Dissertation, University of Colorado. Accessed April 11, 2021. https://scholar.colorado.edu/phys_gradetds/182.

MLA Handbook (7^th Edition):

Grumstrup, Erik Martin. “Elucidation of Ultrafast Photophysics with Optical Pulse Shaping.” 2011. Web. 11 Apr 2021.

Vancouver:

Grumstrup EM. Elucidation of Ultrafast Photophysics with Optical Pulse Shaping. [Internet] [Doctoral dissertation]. University of Colorado; 2011. [cited 2021 Apr 11]. Available from: https://scholar.colorado.edu/phys_gradetds/182.

Council of Science Editors:

Grumstrup EM. Elucidation of Ultrafast Photophysics with Optical Pulse Shaping. [Doctoral Dissertation]. University of Colorado; 2011. Available from: https://scholar.colorado.edu/phys_gradetds/182

		in
And / Or
		in
And / Or
		in
And / Or
		in

Open Access Theses and Dissertations