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Coulomb explosion velocity-map imaging is a new and potentially universal probe for gas-phase chemical dynamics studies, capable of yielding direct information on (time-evolving) molecular structure. The approach relies on a detailed understanding of the mapping between the initial atomic positions within the molecular structure of interest and the final velocities of the fragments formed via Coulomb explosion. Comprehensive on-the-fly ab initio trajectory studies of the Coulomb explosion dynamics are presented for two prototypical small molecules, formyl chloride and cis-1,2-dichloroethene, in order to explore conditions under which reliable structural information can be extracted from fragment velocity-map images. It is shown that for low parent ion charge states, the mapping from initial atomic positions to final fragment velocities is complex and very sensitive to the parent ion charge state as well as many other experimental and simulation parameters. For high-charge states, however, the mapping is much more straightforward and dominated by Coulombic interactions (moderated, if appropriate, by the requirements of overall spin conservation). This study proposes minimum requirements for the high-charge regime, highlights the need to work in this regime in order to obtain robust structural information from fragment velocity-map images, and suggests how quantitative structural information may be extracted from experimental data. [ABSTRACT FROM AUTHOR]

Interest in Criegee intermediates (CIs), often termed carbonyl oxides, and their role in tropospheric chemistry has grown massively since the demonstration of laboratory‐based routes to their formation and characterization in the gas phase. This article reviews current knowledge regarding the electronic spectroscopy of atmospherically relevant CIs like CH2OO, CH3CHOO, (CH3)2COO and larger CIs like methyl vinyl ketone oxide and methacrolein oxide that are formed in the ozonolysis of isoprene, and of selected conjugated carbene‐derived CIs of interest in the synthetic chemistry community. Of the aforementioned atmospherically relevant CIs, all except CH2OO and (CH3)2COO exist in different conformers which, under tropospheric conditions, can display strikingly different thermal loss rates via unimolecular and bimolecular processes. Calculated photolysis rates based on their absorption properties suggest that solar photolysis will rarely be a significant contributor to the total loss rate for any CI under tropospheric conditions. Nonetheless, there is ever‐growing interest in the absorption cross sections and primary photochemistry of CIs following excitation to the strongly absorbing 1ππ* state, and how this varies with CI, with conformer and with excitation wavelength. The later part of this review surveys the photochemical data reported to date, including a range of studies that demonstrate prompt photo‐induced fission of the terminal O–O bond, and speculates about possible alternate decay processes that could occur following non‐adiabatic coupling to, and dissociation from, highly internally excited levels of the electronic ground state of a CI. [ABSTRACT FROM AUTHOR]

The spatial and temporal evolution of the absolute electron densities and temperatures in plasmas formed by nanosecond pulsed laser ablation of silicon in vacuum at two wavelengths (1064 and 532 nm), at similar irradiances, have been explored by complementary simulation (using combined hydrodynamic and adiabatic models) and experiment. Modelling the laser-target and laser-plume interactions with the POLLUX code reveals the evolving composition and dynamics of the laser induced plasma (LIP) during the incident laser pulse: 532 nm irradiation causes more ablation, but the LIP formed by 1064 nm excitation has a higher average charge state and expands faster. The experimental data, from the analysis of Stark broadened line shapes of SiIII and SiIV cations in time-gated, position- and wavelength-resolved images of the plume emission, allow characterisation of the plume dynamics at later times. These dynamics are compared with predictions from two forms of adiabatic expansion model. Both take as input parameters the plume properties returned by the POLLUX simulations for the end of the laser pulse, but differ according to whether the initial plasma is assumed isothermal or isentropic. The study illustrates the important λ-dependences of the target absorption coefficient (in establishing the ablated material density) and of electron–ion inverse bremsstrahlung absorption (in coupling laser radiation into the emergent plasma); the extents to which these interactions, the relative ablation yields, and the plume expansion dynamics depend on λ; and the importance of identifying appropriate initial conditions for adiabatic expansion modelling of LIP in vacuum. [ABSTRACT FROM AUTHOR]

Determining the product velocities offers one of the most direct and penetrating experimental probes of the dynamics of gas phase molecular photodissociation and bimolecular collision processes and provides an obvious point of contact with theoretical molecular dynamics simulations, potential energy surfaces, and non-adiabatic couplings between such surfaces. This perspective traces the development of the H Rydberg atom translational spectroscopy technique from a serendipitous first encounter through to the present, highlights the advances that make it the method of choice for studying many benchmark photofragmentation and photoinduced collision processes that yield H (or D) atoms amongst the products, and anticipates some future opportunities afforded by the technique. [ABSTRACT FROM AUTHOR]

This study of the photodissociation of dimethyl sulfide at λ = 227.5 nm demonstrates the opportunities (and some of the challenges) of product detection using vacuum ultraviolet photoionization combined with recently developed multi-mass imaging methods. The capability of imaging different charged products simultaneously allows determination of the primary fragmentation dynamics through, for example, product fragment momentum and angular distribution matching and reveals potential complications from dissociative ionization, product alignment-dependent photoionization probabilities, and the effects of space charging. [ABSTRACT FROM AUTHOR]

Multi-mass velocity map imaging studies of charged fragments formed by near infrared strong field ionization together with covariance map image analysis offer a new window through which to explore the dissociation dynamics of several different highly charged parent cations, simultaneously – as demonstrated here for the case of CF3IZ+ cations with charges Z ranging from 1 to at least 5. Previous reports that dissociative ionization of CF3I+ cations yields CF3+, I+ and CF2I+ fragment ions are confirmed, and some of the CF3+ fragments are deduced to undergo secondary loss of one or more neutral F atoms. Covariance map imaging confirms the dominance of CF3+ + I+ products in the photodissociation of CF3I2+ cations and, again, that some of the primary CF3+ photofragments can shed one or more F atoms. Rival charge symmetric dissociation pathways to CF2I+ + F+ and to IF+ + CF2+ products and charge asymmetric dissociations to CF3 + I2+ and CF2I2+ + F products are all also identified. The findings for parent cations with Z ≥ 3 are wholly new. In all cases, the fragment recoil velocity distributions imply dissociation dynamics in which coulombic repulsive forces play a dominant role. The major photoproducts following dissociation of CF3I3+ ions are CF3+ and I2+, with lesser contributions from the rival CF2I2+ + F+ and CF32+ + I+ channels. The CF32+ fragment ion images measured at higher incident intensities show a faster velocity sub-group consistent with their formation in tandem with I2+ fragments, from photodissociation of CF3I4+ parent ions. The measured velocity distributions of the I3+ fragment ions contain features attributable to CF3I5+ photodissociation to CF32+ + I3+ and the images of fragments with mass to charge (m/z) ratio ∼31 show formation of I4+ products that must originate from parent ions with yet higher Z. [ABSTRACT FROM AUTHOR]