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

Ultrafast photophysical studies of a multicomponent sunscreen : oxybenzone - titanium dioxide mixtures

Recent studies of the sunscreen constituent oxybenzone have suggested that the dominant mechanism underlying the efficient photoprotection it offers relies on an initial ultrafast enol -> keto tautomerisation, followed by nonadiabatic transfer to the ground electronic state. Subsequent collisions with the solvent bath then reform the original enol tautomer. Utilising femtosecond transient electronic absorption spectroscopy we explore the dissipation of electronic excitation energy in oxybenzone in the presence of titanium dioxide, a widely used, and complementary sunscreen component. We find the relaxation dynamics of this popular organic filter are unaltered by the presence of this favoured inorganic scatterer and the overall dynamics can be described by the additive contribution of the individual constituents. The combination of the two components provides broadband photoprotective properties justifying the widely used organic filter and inorganic scatterer mixtures in commercial sunscreen products

Towards Understanding Photodegradation Pathways in Lignins:The Role of Intramolecular Hydrogen Bonding in Excited States

The photoinduced dynamics of the lignin building blocks syringol, guaiacol, and phenol were studied using time-resolved ion yield spectroscopy and velocity map ion imaging. Following irradiation of syringol and guaiacol with a broad-band femtosecond ultraviolet laser pulse, a coherent superposition of out-of-plane OH torsion and/or OMe torsion/flapping motions is created in the first excited 1ππ* (S1) state, resulting in a vibrational wavepacket, which is probed by virtue of a dramatic nonplanar → planar geometry change upon photoionization from S1 to the ground state of the cation (D0). Any similar quantum beat pattern is absent in phenol. In syringol, the nonplanar geometry in S1 is pronounced enough to reduce the degree of intramolecular H bonding (between OH and OMe groups), enabling H atom elimination from the OH group. For guaiacol, H bonding is preserved after excitation, despite the nonplanar geometry in S1, and prevents O–H bond fission. This behavior affects the propensities for forming undesired phenoxyl radical sites in these three lignin chromophores and provides important insight into their relative “photostabilities” within the larger biopolymer

Substrate surface patterning by optical near field modulation around colloidal particles immersed in a liquid

Optical near field enhancements in the vicinity of particles illuminated by laser light are increasingly recognized as a powerful tool for nanopatterning applications, but achieving sub-wavelength details from the near-field distribution remains a challenge. Here we present a quantitative analysis of the spatial modulation of the near optical fields generated using single 8 ps, 355 nm (and 532 nm) laser pulses around individual colloidal particles and small close packed arrays of such particles on silicon substrates. The analysis is presented for particles in air and, for the first time, when immersed in a range of liquid media. Immersion in a liquid allows detailed exploration of the effects on the near field of changing not just the magnitude but also the sign of the refractive index difference between the particle and the host medium. The level of agreement between the results of ray tracing and Mie scattering simulations, and the experimentally observed patterns on solid surfaces, should encourage further modelling, predictions and demonstrations of the rich palette of sub-wavelength surface profiles that can be achieved using colloidal particles immersed in liquids