The influence of the anion vibrational temperature on the fs dynamics in a NeNePo experiment

Abstract.

A negative-neutral-positive (NeNePo) femtosecond charge-reversal experiment studying the temperature-dependent relaxation dynamics of linear Ag₃ is described. A wavepacket is prepared on the potential-energy surface of the electronic ground state of the neutral trimer by photodetachment from an anion ensemble held at different, well-defined temperatures between 20 K and 350 K. The wavepacket dynamics is probed by resonant two-photon ionization. The cooled octopole ion trap developed to prepare the cold anions is described. The relaxation dynamics of the initially linear Ag₃ from a saddle point of the potential-energy surface into the triangular equilibrium configuration shows a significant dependence on the anion temperature, which is rationalized in terms of a simple model. We demonstrate that a low anion vibrational temperature results in the generation of “narrower” wavepackets on the neutral potential-energy surface. This allows us to probe coherent effects more sensitively.