  We investigate the control of electronic energy transfer in molecular dimers
through the preparation of specific vibrational coherences prior to electronic
excitation, and its observation by nonlinear wave-packet interferometry.
Laser-driven coherent nuclear motion can affect the instantaneous resonance
between site-excited electronic states and thereby influence short-time
electronic excitation transfer (EET). We first illustrate this control
mechanism with calculations on a dimer whose constituent monomers undergo
harmonic vibrations. We then consider the use of nonlinear wave-packet
interferometry (nl-WPI) experiments to monitor the nuclear dynamics
accompanying EET in general dimer complexes following impulsive vibrational
excitation by a sub-resonant control pulse (or control pulse sequence). In
measurements of this kind, two pairs of polarized phase-related femtosecond
pulses following the control pulse 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 derive the basic expression for a
control-pulse-dependent nl-WPI signal. The electronic transition moments of the
constituent monomers are assumed to have a fixed relative orientation, while
the overall orientation of the complex is distributed isotropically. We include
the limiting case of coincident arrival by pulses within each phase-related
pair in which control-influenced nl-WPI reduces to a fluorescence-detected
pump-probe difference experiment. Numerical calculations of pump-probe signals
based on these theoretical expressions are presented in the following paper.
