Development of Ultraviolet-Ultraviolet Hole-Burning Spectroscopy for Cold Gas-Phase Ions

A new ultraviolet-ultraviolet hole-burning (UV-UV HB) spectroscopic scheme has been developed for cold gas-phase ions in a quadrupole ion trap (QIT) connected with a time-of-flight (TOF) mass spectrometer. In this method, a pump UV laser generates a population hole for the ions trapped in the cold QIT, and a second UV laser (probe) monitors the population hole for the ions extracted to the field-free region of the TOF mass spectrometer. Here, the neutral fragments generated by the UV dissociation of the ions with the second laser are detected. This UV-UV HB spectroscopy was applied to protonated dibenzylamine and to protonated uracil. Protonated uracil exhibits two strong electronic transitions; one has a band origin at 31760 cm(-1) and the other at 39000 cm(-1). From the UV-UV HB measurement and quantum chemical calculations, the lower-energy transition is assigned to the enol-keto tautomer and the higher-energy one to the enol-enol tautomer.