Coherent two-dimensional infrared spectroscopy : a study of coupled vibrations
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003.
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| Format: | Thesis |
| Language: | eng |
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Massachusetts Institute of Technology
2005
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| Online Access: | http://hdl.handle.net/1721.1/17653 |
| _version_ | 1811072559237562368 |
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| author | Demirdöven, Nurettin, 1974- |
| author2 | Andrei Tokmanoff. |
| author_facet | Andrei Tokmanoff. Demirdöven, Nurettin, 1974- |
| author_sort | Demirdöven, Nurettin, 1974- |
| collection | MIT |
| description | Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003. |
| first_indexed | 2024-09-23T09:07:51Z |
| format | Thesis |
| id | mit-1721.1/17653 |
| institution | Massachusetts Institute of Technology |
| language | eng |
| last_indexed | 2024-09-23T09:07:51Z |
| publishDate | 2005 |
| publisher | Massachusetts Institute of Technology |
| record_format | dspace |
| spelling | mit-1721.1/176532019-04-10T20:54:28Z Coherent two-dimensional infrared spectroscopy : a study of coupled vibrations Coherent 2-dimensional infrared spectroscopy : a study of coupled vibrations Coherent 2D infrared spectroscopy : a study of coupled vibrations Demirdöven, Nurettin, 1974- Andrei Tokmanoff. Massachusetts Institute of Technology. Dept. of Chemistry. Massachusetts Institute of Technology. Dept. of Chemistry. Chemistry. Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2003. Vita. Includes bibliographical references. This thesis provides an introduction to experimental techniques used in two-dimensional (2D) infrared (IR) spectroscopy, outlines how third-order nonlinear response of a multi-level vibrational system is calculated, and provides a detailed methodology of line shape analysis in 2D spectroscopy. Specific emphasis is given to inherent sensitivity of 2D spectroscopy to correlated spectral broadening. The signatures of highly correlated transition energy fluctuations in a model system of two strongly coupled carbonyl stretching vibrations are reflected by the elongation of the cross peaks along the diagonal of the 2D spectrum. The dynamics of this correlation is monitored by the changes in the 2D line shapes and successfully modeled using a correlated spectral diffusion model. The sensitivity of 2D IR spectroscopy to interactions between multiple vibrational coordinates is also explored in conformationally complex polypeptides and proteins with well-defined secondary structures. 2D IR spectroscopy of β-hairpins and globular proteins with antiparallel (AP) β-sheet domains is studied to identify 2D markers of AP β-sheet conformation. The experiments on β-hairpins and proteins with varying percentage of β-sheet character showed that the formation of cross peaks between the two characteristic vibrational modes of AP β-sheets is a marker of AP β-sheet secondary structure. The intensity, location and line shapes of the cross peaks are qualitatively related to the size, geometry and the conformational variations in the AP β-sheet structure. by Nurettin Demirdöven. Ph.D. 2005-06-02T16:34:11Z 2005-06-02T16:34:11Z 2003 2003 Thesis http://hdl.handle.net/1721.1/17653 55025273 eng M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 257 p. 9824782 bytes 9824581 bytes application/pdf application/pdf application/pdf Massachusetts Institute of Technology |
| spellingShingle | Chemistry. Demirdöven, Nurettin, 1974- Coherent two-dimensional infrared spectroscopy : a study of coupled vibrations |
| title | Coherent two-dimensional infrared spectroscopy : a study of coupled vibrations |
| title_full | Coherent two-dimensional infrared spectroscopy : a study of coupled vibrations |
| title_fullStr | Coherent two-dimensional infrared spectroscopy : a study of coupled vibrations |
| title_full_unstemmed | Coherent two-dimensional infrared spectroscopy : a study of coupled vibrations |
| title_short | Coherent two-dimensional infrared spectroscopy : a study of coupled vibrations |
| title_sort | coherent two dimensional infrared spectroscopy a study of coupled vibrations |
| topic | Chemistry. |
| url | http://hdl.handle.net/1721.1/17653 |
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