Theoretical study of single-molecule spectroscopy and vibrational spectroscopy in condensed phases

In this thesis, theoretical models and computer simulations are employed to study several problems of single-molecule spectroscopy and vibrational spectroscopy in condensed phases. The first part of the thesis concentrates on studying dynamic disorders probed by single molecule fluorescence spectroscopy. Event statistics and correlations of single-molecule fluorescence sequences of modulated reactions are evaluated for multi-channel model, diffusion-controlled reaction model, and stochastic rate model. Several event-related measurements, such as the on-time correlation and the two-event number density, are proposed to map out the memory function, which characterizes the correlation in the conformational fluctuations. A semiflexible Gaussian chain model is used to determine the statistics and correlations of single-molecule fluorescence resonant energy transfer (FRET) experiments on biological polymers. The distribution functions of the fluorescence lifetime and the FRET efficiency provide direct measures of the chain stiffness and their correlation functions probe the intra-chain dynamics at the single-molecule level. The fluorescence lifetime distribution is decomposed into high order memory functions that can be measured in single- molecule experiments. The scaling of the average fluorescence lifetime on the contour length is predicted with the semi-flexible Gaussian chain model and agrees favorably with recent experiments and computer simulations.

Department dc:contributor.department

Massachusetts Institute of Technology. Dept. of Chemistry.

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2005

Author dc:creator

• Yang, Shilong, 1975-

Advisor dc:contributor.advisor

• Jianshu Cao.

• Chemistry.

Statement dc:rights

• 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.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

http://hdl.handle.net/1721.1/30237

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/30237