Theoretical studies of the external vibrational control of electronic excitation transfer and its observation using polarization- and optical phase-sensitive ultrafast spectroscopy

Our theoretical studies involve the control of electronic energy transfer in molecular dimers through the preparation of specific vibrational coherences prior to electronic excitation. Our control strategy is based upon the fact that, following impulsive electronic excitation, nuclear motion acts to change the instantaneous energy difference between site-excited electronic states and thereby influences short-time electronic excitation transfer (EET). By inducing coherent intramolecular vibration in one of the chromophores prior to short-pulse electronic excitation, we exert external control over electronic dynamics.;As a means to monitor this coherent control over EET, we propose using multidimensional wave-packet interferometry (md-WPI). Two pairs of polarized phase-related femtosecond pulses following the control pulse would generate superpositions of coherent nuclear wave packets in optically accessible electronic states. Interference contributions to the time- and frequency-integrated fluorescence signal due to overlaps among the superposed wave packets provide amplitude-level information on the nuclear and electronic dynamics.;We test both the control strategy and its spectroscopic investigation by calculating pump-probe difference signals for various combinations of pulse polarizations. That signal is the limiting case of the control-influenced md-WPI signal in which the two pulses in the pump pulse-pair coincide, as do the two pulses in the probe pulse-pair. We present calculated pump-probe difference signals for a variety of systems including a simplified model of the covalent dimer dithia-anthracenophane (DTA) in which we treat only the weakly Franck-Condon active ν12 anthracene vibration at 385 cm−1. We further present calculated nl-WPI difference signals for an oriented DTA complex, which reveal amplitude-level dynamical information about the interaction of nuclear motion and electronic energy transfer.;We also present pump-probe difference signals from a model system in which a CF3 group, whose torsional angle is strongly Franck-Condon active, has been added to the anthracene monomers which make up DTA. We make use of electronic structure calculations to find the torsional potential of the monomer, from which we calculate the spectroscopic signals of the dimer. We show that a significant measure of control over short-time EET is achievable in this system.;This dissertation includes previously published coauthored material.