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You searched for +publisher:"University of North Carolina" +contributor:("Molesky, Brian"). One record found.

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University of North Carolina

1. Molesky, Brian. Elucidation of Chemical Reactions by Two-Dimensional Resonance Raman Spectroscopy.

Degree: Chemistry, 2016, University of North Carolina

It has been shown for many systems, including photosynthetic complexes, molecule-semiconductor interfaces, and bulk heterojunctions, that interaction between electronic and nuclear dynamics may heavily influence chemical mechanisms. Four-wave-mixing spectroscopies (i.e. transient absorption, two-dimensional spectroscopy) provide some insight into such non-equilibrium processes but are limited by the single “population time” available in these types of experiments. In this dissertation, two-dimensional resonance Raman spectroscopy (2DRR) is developed to obtain new information regarding chemical reactions that possess time coincident electronic and nuclear evolution. These new insights can only be acquired through higher-order techniques possessing two “population times”. Specifically, the coherent reaction mechanism in triiodide photodissociation and structural heterogeneity in myoglobin are investigated. All multidimensional spectroscopies have roots in the off-resonant multidimensional Raman techniques developed from the late 1980’s to the early 2000’s. Throughout their development these experiments were plagued with technical challenges that eventually halted further use. In this dissertation it is shown through rigorous experimental tests that the technical challenges of the past are obviated for 2DRR, which is done under electronically resonant conditions. The key is that under electronic resonance the harmonic character of vibrational modes contributes to the signal. Under off-resonant conditions signal generation depends on much weaker effects. Upon absorption of light ranging from ~250 to ~500 nm triiodide photodissociates into diiodide and radical iodine on the same time scale as the period of triiodide’s symmetric stretch, impulsively initiating coherence in the stretching coordinate of diiodide. In this dissertation, the sensitivity of 2DRR to coherent reaction mechanisms is shown by directly measuring, for the first time, how the nonequilibrium geometry of triiodide at the moment of photodissociation determines the stretching frequency of diiodide. The functions of heme proteins involve ligand binding and dissociation events, which are facilitated by the fast exchange of energy between the heme and aqueous solvent. It is known that the heme’s propionic acid side chains act as an effective “gateway” for this fast energy exchange. In this dissertation it is shown that the propionic chains within myoglobin posses significant structural heterogeneity, suggesting that this may be an important factor in facilitating the functions of heme proteins. Advisors/Committee Members: Molesky, Brian, Moran, Andrew, Kanai, Yosuke, Atkin, Joanna, Cahoon, James, Warren, Scott.

Subjects/Keywords: College of Arts and Sciences; Department of Chemistry

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

APA (6th Edition):

Molesky, B. (2016). Elucidation of Chemical Reactions by Two-Dimensional Resonance Raman Spectroscopy. (Thesis). University of North Carolina. Retrieved from https://cdr.lib.unc.edu/record/uuid:57b9e2e7-71d5-48e8-837c-e1e1b21774a9

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16th Edition):

Molesky, Brian. “Elucidation of Chemical Reactions by Two-Dimensional Resonance Raman Spectroscopy.” 2016. Thesis, University of North Carolina. Accessed December 01, 2020. https://cdr.lib.unc.edu/record/uuid:57b9e2e7-71d5-48e8-837c-e1e1b21774a9.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7th Edition):

Molesky, Brian. “Elucidation of Chemical Reactions by Two-Dimensional Resonance Raman Spectroscopy.” 2016. Web. 01 Dec 2020.

Vancouver:

Molesky B. Elucidation of Chemical Reactions by Two-Dimensional Resonance Raman Spectroscopy. [Internet] [Thesis]. University of North Carolina; 2016. [cited 2020 Dec 01]. Available from: https://cdr.lib.unc.edu/record/uuid:57b9e2e7-71d5-48e8-837c-e1e1b21774a9.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Molesky B. Elucidation of Chemical Reactions by Two-Dimensional Resonance Raman Spectroscopy. [Thesis]. University of North Carolina; 2016. Available from: https://cdr.lib.unc.edu/record/uuid:57b9e2e7-71d5-48e8-837c-e1e1b21774a9

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

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