Protonation isomers of gas-phase nicotineH+ are separated and assigned using a combination of FAIMS and UV photodissociation action spectroscopy.

The influence of oriented electric fields on chemical reactivity and photochemistry is an area of increasing interest. Within a molecule, different protonation sites offer the opportunity to control the location of charge and thus orientation of electric fields. New techniques are thus needed to discriminate between protonation isomers in order to understand this effect. This investigation reports the UV-photodissociation action spectroscopy of two protonation isomers (protomers) of 1,3-diazanaphthalene (quinazoline) arising from protonation of a nitrogen at either the 1- or 3-position. It is shown that these protomers are separable by field-asymmetric ion mobility spectrometry (FAIMS) with confirmation provided by UV-photodissociation (PD) action spectroscopy. Vibronic features in the UVPD action spectra and computational input allow assignment of the origin transitions to the S1 and S5 states of both protomers. These experiments also provide vital benchmarks for protomer-specific calculations and examination of isomer-resolved reaction kinetics and thermodynamics.

The low-lying electronic states of Irgacure 2959, a Norrish-type I photoinitiator, complexed with a single metal cation are investigated in the gas-phase by photodissociation action spectroscopy. Analysis of the band-shifts using quantum chemical calculations (TD-DFT and SCS-CC2) reveals the underlying influence of the charge on the key electronic energy levels. Since the

Ultraviolet-photodissociation (UVPD) mass spectrometry is an emerging analytical tool for structural elucidation of biomolecules including lipids. Gas phase UVPD of ionised fatty acids (FAs) can promote fragmentation that is diagnostic...

Infrared and electronic spectra are indispensable for understanding the structural and energetic properties of charged molecules and clusters in the gas phase. However, the presence of isomers can potentially complicate the interpretation of spectra, even if the target molecules or clusters are mass-selected beforehand. Here, we describe an instrument for spectroscopically characterizing charged molecular clusters that have been selected according to both their isomeric form and their mass-to-charge ratio. Cluster ions generated by laser ablation of a solid sample are selected according to their collision cross sections with helium buffer gas using a drift tube ion mobility spectrometer and their mass-to-charge ratio using a quadrupole mass filter. The mobility- and mass-selected target ions are introduced into a cryogenically cooled, three-dimensional quadrupole ion trap where they are thermalized through inelastic collisions with an inert buffer gas (He or He/N2 mixture). Spectra of the molecular ions are obtained by tagging them with inert atoms or molecules (Ne and N2), which are dislodged following resonant excitation of an electronic transition, or by photodissociating the cluster itself following absorption of one or more photons. An electronic spectrum is generated by monitoring the charged photofragment yield as a function of wavelength. The capacity of the instrument is illustrated with the resonance-enhanced photodissociation action spectra of carbon clusters ([Formula: see text]) and polyacetylene cations (HC2 nH+) that have been selected according to the mass-to-charge ratio and collision cross section with He buffer gas and of mass-selected [Formula: see text] and Au2Ag+ clusters.