We describe the preparation of diatomic trications using intense femtosecond laser pulses, and discuss the feasibility of using femtoseond pump-probe techniques to measure the vibrational spectrum of Cl-2(3+). Initial attempts to observe the vibrational spectra of Cl-2(3+) were unsuccessful. Possible refinements to the experiment are guided by calculations of the electronic states, transition moments, and field-dressed potential curves for Cl-2(3+). Solution of the time-dependent Schrodinger equation; using these theoretical data as input allow an accurate simulation of pump-probe experiments and their time-delay signals. Optimization of the experimental parameters via the simulation suggests an improved approach to obtaining the spectra of trications, with special emphasis on the unusual aspects of these systems.