Theoretical study of single-molecule spectroscopy and vibrational spectroscopy in condensed phases
2005
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. To interpret the fluorescence measurements
of the mechanical properties of double-stranded DNA, a worm-like
chain model is used as a first-principle model to study
double-stranded DNA under hydrodynamic flows. The second part of
the thesis concentrates on nonperturbative vibrational energy
relaxation (VER) effects of vibrational line shapes. In general,
nonperturbative and non-Markovian VER effects are demonstrated more
strongly on nonlinear vibrational line shapes than on linear
absorption.
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