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C–I bond extension and fission following ultraviolet (UV, 262 nm) photoexcitation of 2- and 3-iodothiophene is studied using ultrafast time-resolved extreme ultraviolet (XUV) ionization in conjunction with velocity map ion imaging. The photoexcited molecules and eventual I atom products are probed by site-selective ionization at the I 4d edge using intense XUV pulses, which induce multiple charges initially localized to the iodine atom. At C–I separations below the critical distance for charge transfer (CT), charge can redistribute around the molecule leading to Coulomb explosion and charged fragments with high kinetic energy. At greater C–I separations, beyond the critical distance, CT is no longer possible and the measured kinetic energies of the charged iodine atoms report on the neutral dissociation process. The time and momentum resolved measurements allow determination of the timescales and the respective product momentum and kinetic energy distributions for both isomers, which are interpreted in terms of rival 'direct' and 'indirect' dissociation pathways. The measurements are compared with a classical over the barrier model, which reveals that the onset of the indirect dissociation process is delayed by ∼1 ps relative to the direct process. The kinetics of the two processes show no discernible difference between the two parent isomers, but the branching between the direct and indirect dissociation channels and the respective product momentum distributions show isomer dependencies. The greater relative yield of indirect dissociation products from 262 nm photolysis of 3-iodothiophene (cf. 2-iodothiophene) is attributed to the different partial cross-sections for (ring-centred) π∗ ← π and (C–I bond localized) σ∗ ← (n/π) excitation in the respective parent isomers. [ABSTRACT FROM AUTHOR]

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]

Wavelength-dependent measurements of the RNA base uracil, undertaken with nanosecond ultraviolet laser pulses, have previously identified a fragment at m/z = 84 (corresponding to the C3H4N2O+ ion) at excitation wavelengths ≤232 nm. This has been interpreted as a possible signature of a theoretically predicted ultrafast ring-opening occurring on a neutral excited state potential energy surface. To further investigate the dynamics of this mechanism, and also the non-adiabatic dynamics operating more generally in uracil, we have used a newly built ultra-high vacuum spectrometer incorporating a laser-based thermal desorption source to perform time-resolved ion-yield measurements at pump wavelengths of 267 nm, 220 nm, and 200 nm. We also report complementary data obtained for the related species 2-thiouracil following 267 nm excitation. Where direct comparisons can be made (267 nm), our findings are in good agreement with the previously reported measurements conducted on these systems using cold molecular beams, demonstrating that the role of initial internal energy on the excited state dynamics is negligible. Our 220 nm and 200 nm data also represent the first reported ultrafast study of uracil at pump wavelengths <250 nm, revealing extremely rapid (<200 fs) relaxation of the bright S3(1ππ*) state. These measurements do not, however, provide any evidence for the appearance of the m/z = 84 fragment within the first few hundred picoseconds following excitation. This key finding indicates that the detection of this specific species in previous nanosecond work is not directly related to an ultrafast ring-opening process. An alternative excited state process, operating on a more extended time scale, remains an open possibility. [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]

Time-resolved photoelectron imaging was used to investigate the electronic relaxation dynamics of gas-phase aniline, N, N-dimethylaniline, and 3,5-dimethylaniline following ultraviolet excitation at 250 nm. Our analysis was supported by ab initio coupled-cluster calculations evaluating excited state energies and (in aniline) the evolution of a range of excited state physical properties as a function of N-H bond extension. Due to a lack of consistency between several earlier studies undertaken in aniline, the specific aim of this present work was to gain new insight into the previously proposed non-adiabatic coupling interaction between the two lowest lying singlet excited states S1(ΠΠ*) and S2(3s/Πσ*). The methyl-substituted systems N, N-dimethylaniline and 3,5-dimethylaniline were included in order to obtain more detailed dynamical information about the key internal molecular coordinates that drive the S1(ΠΠ*)/S2(3s/Πσ*) coupling mechanism. Our findings suggest that in all three systems, both electronic states are directly populated during the initial excitation, with the S2(3s/Πσ*) state then potentially decaying via either direct dissociation along the N-X stretching coordinate (X = H or CH3) or internal conversion to the S1(ΠΠ*) state. In aniline and N, N-dimethylaniline, both pathways most likely compete in the depletion of S2(3s/Πσ*) state population. However, in 3,5-dimethylaniline, only the direct dissociation mechanism appears to be active. This is rationalized in terms of changes in the relative rates of the two decay pathways upon methylation of the aromatic ring system. [ABSTRACT FROM AUTHOR]

Photochemistry plays a significant role in shaping the chemical reaction network in the solar nebula and interstellar clouds. However, even in a simple triatomic molecule photodissociation, determination of all fragmentation processes is yet to be achieved. In this work, we present a comprehensive study of the photochemistry of H 2 S, derived from cutting-edge translational spectroscopy measurements of the H, S( 1 D) and S( 1 S) atom products formed by photolysis at wavelengths across the range 155-120 nm. The results provide detailed insights into the energy disposal in the SH( X ), SH( A ) and H 2 co-fragments, and the atomisation routes leading to two H atoms along with S( 3 P) and S( 1 D) atoms. Theoretical calculations allow the dynamics of all fragmentation processes, especially the bimodal internal energy distributions in the diatomic products, to be rationalised in terms of non-adiabatic transitions between potential energy surfaces of both 1 A' and 1 A'' symmetry. The comprehensive picture of the wavelength-dependent (or vibronic state-dependent) photofragmentation behaviour of H 2 S will serve as a text-book example illustrating the importance of non-Born-Oppenheimer effects in molecular photochemistry, and the findings should be incorporated in future astrochemical modelling., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)