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

We report on a form of gas-phase anion action spectroscopy based on infrared multiple photon electron detachment and subsequent capture of the free electrons by a neutral electron scavenger in a Fourier Transform Ion Cyclotron Resonance (FTICR) mass spectrometer. This method allows one to obtain background-free spectra of strongly bound anions, for which no dissociation channels are observed. The first gas-phase spectra of acetate and propionate are presented using SF6 as electron scavenger and a free electron laser as source of intense and tunable infrared radiation. To validate the method, we compare infrared spectra obtained through multiple photon electron detachment/attachment and multiple photon dissociation for the benzoate anion. In addition, different electron acceptors are used, comparing both associative and dissociative electron capture. The relative energies of dissociation (by CO2 loss) and electron detachment are investigated for all three anions by DFT and CCSD(T) methods. DFT calculations are also employed to predict vibrational frequencies, which provide a good fit to the infrared spectra observed. The frequencies of the symmetric and antisymmetric carboxylate stretching modes for the aliphatic carboxylates are compared to those previously observed in condensed-phase IR spectra and to those reported for gas-phase benzoate, showing a strong influence of the solution environment and a slight substituent effect on the antisymmetric stretch.Comment: Revised version, Submitted to J Phys Chem

Electron stimulated desorption of anions containing Oxygen and Nitrogen from self-assembled monolayers of DNA

The electron stimulated desorption of anions from self-assembled monolayers of double stranded DNA is reported. Desorption of the oxygen and nitrogen containing anions O−, OH−, CN−, OCN−, and OCNH− is induced by the impact of 0.1−20 eV electrons. The anion desorption yields, measured as a function of incident electron energy exhibit pronounced maxima that can be attributed to dissociative electron attachment (DEA) to basic DNA units. Above 15 eV, desorption is attributed to dipolar dissociation (DD). This study further indicates that electrons with energy as low as 2.5 ± 0.3 eV can not only cause damage to DNA but also produce fragments with considerable kinetic energy

Dissociation of dicarboxylate and disulfonate dianions

Collision-induced dissociation (CID), along with infrared multiple photon dissociation/detachment (IRMPD) techniques, is utilized to study a series of doubly substituted aromatic dianions containing sulfonate and carboxylate functionalities (1,2- and 1,3-benzenedisulfonate, 1,5-naphthalenedisulfonate, 2,6-naphthalenedisulfonate, 4-sulfobenzoate, 2,6-naphthalenedicarboxylate, and terephthalate dianions). The molecules were chosen because of the electronegativity of the C

Electron Energy Loss and One- and Two-Photon Excited SERS Probing of “Hot” Plasmonic Silver Nanoaggregates

We report electron energy loss spectroscopy (EELS) and one- and two-photon excited surface-enhanced Raman scattering (SERS) and hyper Raman studies on plasmonic silver nanoaggregates. By comparison with computations, EELS imaging reveals an inverse relationship between local field intensity in an optical experiment and electron energy loss intensity at energies corresponding to excitation wavelengths used for optical probing. This inverse relation exists independent on specific nanoaggregate geometries and is mainly controlled by the gap size between the particles forming the aggregate. The ratio between two- and one-photon excited SERS measured at different excitation wavelengths provides information about local fields in the hottest spots and their dependence on the photon energy. Our data verify experimentally the predicted increase of local optical fields in the hot spots with increasing wave lengths. The reported findings show new experimental ways to characterize local fields of plasmonic nanostructures. This is of particular importance for complex structures which are not easily approachable by computations