Millar, David Philip (1982) Picosecond studies of molecular energy transfer, reorientation, and internal motion dynamics. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-04042008-131831
NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. This thesis describes the development and characterization of mode- locked CW dye lasers and their application to time-resolved studies of molecular reorientation in liquids, electronic energy transfer in solution, and the internal motions of nucleic acids. Both passive and synchronous mode-locking are found to produce slightly structured pulses with coherence times [...], and pulse envelope widths [...]. The dynamics of reorientation of cresyl violet in alcohol solvents is directly studied on the picosecond time scale. The observed rotational correlation function decays as a single exponential, with a rotational relaxation time that is linearly dependent on solvent viscosity. Rotation times calculated from hydrodynamics are a factor of 2 smaller than observed. The discrepancy is attributed to hydrogen-bonding interactions with the solvent that cause additional friction. Electronic energy transfer between cresyl violet donors and azulene acceptors in solution is studied. The excited donor decay is in excellent agreement with the Rirster dipole-dipole model over the time range from 2 psec to 10 nsec. The critical transfer distance inferred from the decay [...] agrees well with the value calculated from the spectral properties, [...]. The increased energy transfer rate in fluid solutions due to translational motion is accurately predicted by the approximate solution to a diffusion equation for the donor excitation. However, the energy transport due to donor-donor transfer was nondiffusive on the picosecond time scale. The dynamics of the torsional and bending motions of nucleic acids are studied by sub-nanosecond time-dependent fluorescence depolarization of intercalated ethidium bromide. The non-exponential relaxation behavior is observed for the first time, and is in excellent agreement with the theoretical predictions of an elastic model for DNA internal motions. The intrinsic torsional rigidity of calf thymus DNA is [...] erg.cm. The torsional rigidity is shown to be sensitive to details of primary, secondary, and tertiary nucleic acid structure. The polyelectrolyte contribution to the torsional rigidity of DNA has been measured for the first time.
|Item Type:||Thesis (Dissertation (Ph.D.))|
|Degree Grantor:||California Institute of Technology|
|Division:||Chemistry and Chemical Engineering|
|Awards:||The Herbert Newby McCoy Award, 1981|
|Thesis Availability:||Public (worldwide access)|
|Defense Date:||19 March 1982|
|Default Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Imported from ETD-db|
|Deposited On:||04 Apr 2008|
|Last Modified:||26 Dec 2012 02:36|
- Final Version
See Usage Policy.
Repository Staff Only: item control page