Fragmentation dynamics of the ethyl bromide and ethyl iodide cations: a velocity-map imaging study

The photodissociation dynamics of ethyl bromide and ethyl iodide cations (C2H5Br+ and C2H5I+) have been studied. Ethyl halide cations were formed through vacuum ultraviolet (VUV) photoionization of the respective neutral parent molecules at 118.2 nm, and were photolysed at a number of ultraviolet (UV) photolysis wavelengths, including 355 nm and wavelengths in the range from 236 to 266 nm. Time-of-flight mass spectra and velocity-map images have been acquired for all fragment ions and for ground (Br) and spin–orbit excited (Br*) bromine atom products, allowing multiple fragmentation pathways to be investigated. The experimental studies are complemented by spin–orbit resolved ab initio calculations of cuts through the potential energy surfaces (along the RC–Br/I stretch coordinate) for the ground and first few excited states of the respective cations. Analysis of the velocity-map images indicates that photoexcited C2H5Br+ cations undergo prompt C–Br bond fission to form predominantly C2H5+ + Br* products with a near-limiting ‘parallel’ recoil velocity distribution. The observed C2H3+ + H2 + Br product channel is thought to arise via unimolecular decay of highly internally excited C2H5+ products formed following radiationless transfer from the initial excited state populated by photon absorption. Broadly similar behaviour is observed in the case of C2H5I+, along with an additional energetically accessible C–I bond fission channel to form C2H5 + I+ products. HX (X = Br, I) elimination from the highly internally excited C2H5X+ cation is deemed the most probable route to forming the C2H4+ fragment ions observed from both cations. Finally, both ethyl halide cations also show evidence of a minor C–C bond fission process to form CH2X+ + CH3 products

Time-resolved multi-mass ion imaging: femtosecond UV-VUV pump-probe spectroscopy with the PImMS camera

The Pixel-Imaging Mass Spectrometry (PImMS) camera allows for 3D charged particle imaging measurements, in which the particle time-of-flight is recorded along with $(x,y)$ position. Coupling the PImMS camera to an ultrafast pump-probe velocity-map imaging spectroscopy apparatus therefore provides a route to time-resolved multi-mass ion imaging, with both high count rates and large dynamic range, thus allowing for rapid measurements of complex photofragmentation dynamics. Furthermore, the use of vacuum ultraviolet wavelengths for the probe pulse allows for an enhanced observation window for the study of excited state molecular dynamics in small polyatomic molecules having relatively high ionization potentials. Herein, preliminary time-resolved multi-mass imaging results from C$_2$F$_3$I photolysis are presented. The experiments utilized femtosecond UV and VUV (160.8~nm and 267~nm) pump and probe laser pulses in order to demonstrate and explore this new time-resolved experimental ion imaging configuration. The data indicates the depth and power of this measurement modality, with a range of photofragments readily observed, and many indications of complex underlying wavepacket dynamics on the excited state(s) prepared

Photofragmentation dynamics of <i>N,N</i>-dimethylformamide following excitation at 193 nm

N,N-dimethylformamide, HCON(CH3)2, is a useful model compound for investigating peptide bond photofragmentation dynamics. We report data from a comprehensive experimental and theoretical study into the photofragmentation dynamics of N,N-dimethylformamide in the gas phase at 193 nm. Through a combination of velocity-map imaging and hydrogen atom Rydberg tagging photofragment translational spectroscopy, we have identified two primary fragmentation channels, namely fission of the NCO `peptide' bond, and NCH3 bond fission leading to loss of CH3. The possible fragmentation channels leading to the observed products are rationalised with recourse to CASPT2 calculations of the ground and first few excited-state potential energy curves along the relevant dissociation coordinates, and the results are compared with data from previous experimental and theoretical studies on the same system

Evidence for concerted ring opening and C-Br bond breaking in UV-excited bromocyclopropane

Photodissociation of gaseous bromocyclopropane via its A-band continuum has been studied at excitation wavelengths ranging from 230 nm to 267 nm. Velocity-map images of ground-state bromine atoms (Br), spin-orbit excited bromine atoms (Br*) and C3H5 hydrocarbon radicals reveal the kinetic energies of these various photofragments. Both Br and Br* atoms are predominantly generated via repulsive excited electronic states in a prompt photodissociation process in which the hydrocarbon co-fragment is a cyclopropyl radical. However, the images obtained at the mass of the hydrocarbon radical fragment identify a channel with total kinetic energy greater than that deduced from the Br and Br* images, and with a kinetic energy distribution that exceeds the energetic limit for Br + cyclopropyl radical products. The velocity-map images of these C3H5 fragments have lower angular anisotropies than measured for Br and Br*, indicating molecular restructuring during dissociation. The high kinetic energy C3H5 signals are assigned to allyl radicals generated by a minor photochemical pathway which involves concerted C-Br bond dissociation and cyclopropyl ring-opening following single UV-photon absorption. Slow photofragments also contribute to the velocity map images obtained at the C3H5 radical mass, but corresponding slow Br atoms are not observed. These features in the images are attributed to C3H5+ from the photodissociation of the C3H5Br+ molecular cation following two-photon ionization of the parent compound. This assignment is confirmed by 118-nm vacuum ultraviolet ionization studies that prepare the molecular cation in its ground electronic state prior to UV photodissociation

Exploring machine learning in chemistry through the classification of spectra: an undergraduate project

Applications of machine learning in chemistry are many and varied, from prediction of structure–property relationships, to modeling of potential energy surfaces for large scale atomistic simulations. We describe a generalized approach for the application of machine learning to the classification of spectra which can be used as the basis for a wide variety of undergraduate projects. While our examples use FTIR and mass spectra, the approach could equally well be used with UV–visible, Raman, NMR, or indeed any other type of spectra. We summarize a number of different unsupervised and supervised machine learning algorithms that can be used to classify spectra into groups, and illustrate their application using data from three different projects carried out by fourth year chemistry undergraduates. The three projects investigated the ability of the various machine learning approaches to correctly classify spectra of a variety of fruits, whiskies, and teas, respectively. In all cases the algorithms were able to differentiate between the various samples used in each study, and the trained machine learning models could then be used to classify unknown samples with a high degree of accuracy (>98% in many cases). Depending on the extent to which students are expected to write their own code to perform the data analysis, the general model adopted in this work can be adapted for a variety of purposes, from short (one to two day) practical exercises and workshops, to much longer independent student projects

Development of high throughput microscope mode secondary ion mass spectrometry imaging

This paper describes the development and initial results from a secondary ion mass spectrometer coupled with microscope mode detection. Stigmatic ion microscope imaging enables us to decouple the primary ion (PI) beam focus from spatial resolution and is a promising route to attaining higher throughput for mass spectrometry imaging (MSI). Using a commercial C60+ PI beam source, we can defocus the PI beam to give uniform intensity across a 2.5 mm2 area. By coupling the beam with a position-sensitive spatial detector, we can achieve mass spectral imaging of positive and negative secondary ions (SIs), which we demonstrate using samples comprising metals and dyes. Our approach involves simultaneous desorption of ions across a large field of view, enabling mass spectral images to be recorded over an area of 2.5 mm2 in a matter of seconds. Our instrument can distinguish spatial features with a resolution of better than 20 μm, and has a mass resolution of >500 at 500 u. There is considerable scope to improve this, and through simulations we estimate the future performance of the instrument

Whispering Gallery Modes in Standard Optical Fibres for Fibre Profiling Measurements and Sensing of Unlabelled Chemical Species

Whispering gallery mode resonances in liquid droplets and microspheres have attracted considerable attention due to their potential uses in a range of sensing and technological applications. We describe a whispering gallery mode sensor in which standard optical fibre is used as the whispering gallery mode resonator. The sensor is characterised in terms of the response of the whispering gallery mode spectrum to changes in resonator size, refractive index of the surrounding medium, and temperature, and its measurement capabilities are demonstrated through application to high-precision fibre geometry profiling and the detection of unlabelled biochemical species. The prototype sensor is capable of detecting unlabelled biomolecular species in attomole quantities