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We report on a form of gas-phase anion action spectroscopy based on infraredmultiple photon electron detachment and subsequent capture of the freeelectrons by a neutral electron scavenger in a Fourier Transform Ion CyclotronResonance (FTICR) mass spectrometer. This method allows one to obtainbackground-free spectra of strongly bound anions, for which no dissociationchannels are observed. The first gas-phase spectra of acetate and propionateare presented using SF6 as electron scavenger and a free electron laser assource of intense and tunable infrared radiation. To validate the method, wecompare infrared spectra obtained through multiple photon electrondetachment/attachment and multiple photon dissociation for the benzoate anion.In addition, different electron acceptors are used, comparing both associativeand dissociative electron capture. The relative energies of dissociation (byCO2 loss) and electron detachment are investigated for all three anions by DFTand CCSD(T) methods. DFT calculations are also employed to predict vibrationalfrequencies, which provide a good fit to the infrared spectra observed. Thefrequencies of the symmetric and antisymmetric carboxylate stretching modes forthe aliphatic carboxylates are compared to those previously observed incondensed-phase IR spectra and to those reported for gas-phase benzoate,showing a strong influence of the solution environment and a slight substituenteffect on the antisymmetric stretch.

Action spectroscopy of gas-phase carboxylate anions by multiple photon IR electron detachment/attachment