Vibrational response of adsorbates to femtosecond metal substrate heating

This thesis discusses the use of IR spectroscopy to probe the vibrations of adsorbate molecules following impulsive excitation of electrons in underlying metal substrates by femtosecond visible light pulses. In these experiments the dominant spectral changes observed result from temperature dependent shifts of the oscillator complex frequency. Using the Liouville equation, a general description of the optical response is developed and discussed in the context of an impulsive change in frequency. As low frequency adsorbate-like modes become excited via coupling to substrate electrons and phonons, the high frequency modes are observed to experience frequency shifts. These couplings are described in terms of a Brownian oscillator model. Time-resolved measurements of the stretch mode absorption for CO on copper indicate that couplings of a low frequency vibration to both substrate reservoirs are significant. The coupling rates were determined separately as a result of the dramatic differences in the electronic and phonon temperature profiles. The effects of excitation pulse fluence on vibrational energy transfer between the CO low frequency frustrated translation and metal substrate electrons are examined. A temperature dependent coupling rate is extracted from our data using a dynamical charge transfer model