Quantum State-Dependent Fragmentation Dynamics of D2S Molecules Following Excitation at Wavelengths ∼ 129.1 and ∼ 139.1 nm.

The first high-resolution translational spectroscopy studies of D atom photoproducts following excitation to the Rydberg states of D2S are reported. Excitation at wavelengths λ ∼ 139.1 nm reveals an unusual 'inverse' isotope effect; the 1B1(3da1←2b1) Rydberg state of D2S predissociates much faster than its counterpart in H2S. This is attributed to accidental near resonance with a vibrationally excited level of a lower-lying, more heavily predissociated Rydberg state of D2S that boosts the probability of nonadiabatic coupling to the dissociation continuum with 1A″ symmetry. Excitation at λ ∼ 129.1 nm populates the 1B1(4da1←2b1) Rydberg state, which predissociates more slowly and allows the study of ways in which the branching into different quantum states of the SD products varies with the choice of parent excited (JKaKc) level. All excited parent levels yield both ground (X) and electronically excited (A) state SD fragments. The former are distributed over a wide range of rovibrational (v″, N″) levels, while the population of levels with low v' and high N' is favored in the latter. These trends reflect the topographies of the dissociative 1A″ (1A') potential energy surfaces that correlate with the respective dissociation limits. Rotational motion about the b-inertial axis in the excited state molecule increases the relative yield of SD(A) products, consistent with dissociation by rotationally (Coriolis-) induced coupling from the photoexcited Rydberg level to the 1A' continuum. Molecules excited to the rotationless (JKaKc = 000) level also yield some SD(A) products, however, confirming the operation of a rival fragmentation pathway wherein photoexcited molecules decay by initial vibronic coupling to the 1A″ continuum, with subsequent nonadiabatic coupling between the 1A″ and 1A' continua enabling access to the D + SD(A) limit.

The Role of Momentum Partitioning in Covariance Ion Imaging Analysis.

We present results from a covariance ion imaging study, which employs extensive filtering, on the relationship between fragment momenta to gain deeper insight into photofragmentation dynamics. A new data analysis approach is introduced that considers the momentum partitioning between the fragments of the breakup of a molecular polycation to disentangle concurrent fragmentation channels, which yield the same ion species. We exploit this approach to examine the momentum exchange relationship between the products, which provides direct insight into the dynamics of molecular fragmentation. We apply these techniques to extensively characterize the dissociation of 1-iodopropane and 2-iodopropane dications prepared by site-selective ionization of the iodine atom using extreme ultraviolet intense femtosecond laser pulses with a photon energy of 95 eV. Our assignments are supported by classical simulations, using parameters largely obtained directly from the experimental data.

Unraveling the Rich Fragmentation Dynamics Associated with S-H Bond Fission Following Photoexcitation of H2S at Wavelengths ∼129.1 nm.

H2S is being detected in the atmospheres of ever more interstellar bodies, and photolysis is an important mechanism by which it is processed. Here, we report H Rydberg atom time-of-flight measurements following the excitation of H2S molecules to selected rotational (JKaKc') levels of the 1B1 Rydberg state associated with the strong absorption feature at wavelengths of λ ∼ 129.1 nm. Analysis of the total kinetic energy release spectra derived from these data reveals that all levels predissociate to yield H atoms in conjunction with both SH(A) and SH(X) partners and that the primary SH(A)/SH(X) product branching ratio increases steeply with ⟨Jb2⟩, the square of the rotational angular momentum about the b-inertial axis in the excited state. These products arise via competing homogeneous (vibronic) and heterogeneous (Coriolis-induced) predissociation pathways that involve coupling to dissociative potential energy surfaces (PES(s)) of, respectively, 1A″ and 1A' symmetries. The present data also show H + SH(A) product formation when exciting the JKaKc' = 000 and 111 levels, for which ⟨Jb2⟩ = 0 and Coriolis coupling to the 1A' PES(s) is symmetry forbidden, implying the operation of another, hitherto unrecognized, route to forming H + SH(A) products following excitation of H2S at energies above ∼9 eV. These data can be expected to stimulate future ab initio molecular dynamic studies that test, refine, and define the currently inferred predissociation pathways available to photoexcited H2S molecules.

Exploring the ultrafast and isomer-dependent photodissociation of iodothiophenes via site-selective ionization.

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.

Monitoring the Evolution of Relative Product Populations at Early Times during a Photochemical Reaction.

Identifying multiple rival reaction products and transient species formed during ultrafast photochemical reactions and determining their time-evolving relative populations are key steps toward understanding and predicting photochemical outcomes. Yet, most contemporary ultrafast studies struggle with clearly identifying and quantifying competing molecular structures/species among the emerging reaction products. Here, we show that mega-electronvolt ultrafast electron diffraction in combination with ab initio molecular dynamics calculations offer a powerful route to determining time-resolved populations of the various isomeric products formed after UV (266 nm) excitation of the five-membered heterocyclic molecule 2(5H)-thiophenone. This strategy provides experimental validation of the predicted high (∼50%) yield of an episulfide isomer containing a strained three-membered ring within ∼1 ps of photoexcitation and highlights the rapidity of interconversion between the rival highly vibrationally excited photoproducts in their ground electronic state.

Valence shell electronically excited states of norbornadiene and quadricyclane.

The absolute photoabsorption cross sections of norbornadiene (NBD) and quadricyclane (QC), two isomers with chemical formula C7H8 that are attracting much interest for solar energy storage applications, have been measured from threshold up to 10.8 eV using the Fourier transform spectrometer at the SOLEIL synchrotron radiation facility. The absorption spectrum of NBD exhibits some sharp structure associated with transitions into Rydberg states, superimposed on several broad bands attributable to valence excitations. Sharp structure, although less pronounced, also appears in the absorption spectrum of QC. Assignments have been proposed for some of the absorption bands using calculated vertical transition energies and oscillator strengths for the electronically excited states of NBD and QC. Natural transition orbitals indicate that some of the electronically excited states in NBD have a mixed Rydberg/valence character, whereas the first ten excited singlet states in QC are all predominantly Rydberg in the vertical region. In NBD, a comparison between the vibrational structure observed in the experimental 11B1-11A1 (3sa1 ← 5b1) band and that predicted by Franck-Condon and Herzberg-Teller modeling has necessitated a revision of the band origin and of the vibrational assignments proposed previously. Similar comparisons have encouraged a revision of the adiabatic first ionization energy of NBD. Simulations of the vibrational structure due to excitation from the 5b2 orbital in QC into 3p and 3d Rydberg states have allowed tentative assignments to be proposed for the complex structure observed in the absorption bands between ∼5.4 and 7.0 eV.

Ultrafast electronic relaxation pathways of the molecular photoswitch quadricyclane.

The light-induced ultrafast switching between molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Prior work observed signatures of ultrafast molecular dynamics in both isomers upon ultraviolet excitation but could not follow the electronic relaxation all the way back to the ground state experimentally. Here we study the electronic relaxation of quadricyclane after exciting in the ultraviolet (201 nanometres) using time-resolved gas-phase extreme ultraviolet photoelectron spectroscopy combined with non-adiabatic molecular dynamics simulations. We identify two competing pathways by which electronically excited quadricyclane molecules relax to the electronic ground state. The fast pathway (<100 femtoseconds) is distinguished by effective coupling to valence electronic states, while the slow pathway involves initial motions across Rydberg states and takes several hundred femtoseconds. Both pathways facilitate interconversion between the two isomers, albeit on different timescales, and we predict that the branching ratio of norbornadiene/quadricyclane products immediately after returning to the electronic ground state is approximately 3:2.

Exploring the vacuum ultraviolet photochemistry of astrochemically important triatomic molecules.

The recently constructed vacuum ultraviolet (VUV) free electron laser (FEL) at the Dalian Coherent Light Source (DCLS) is yielding a wealth of new and exquisitely detailed information about the photofragmentation dynamics of many small gas-phase molecules. This Review focuses particular attention on five triatomic molecules-H2O, H2S, CO2, OCS and CS2. Each shows excitation wavelength-dependent dissociation dynamics, yielding photofragments that populate a range of electronic and (in the case of diatomic fragments) vibrational and rotational quantum states, which can be characterized by different translational spectroscopy methods. The photodissociation of an isolated molecule from a well-defined initial quantum state provides a lens through which one can investigate how and why chemical reactions occur, and provides numerous opportunities for fruitful, synergistic collaborations with high-level ab initio quantum chemists. The chosen molecules, their photofragments and the subsequent chemical reaction networks to which they can contribute are all crucial in planetary atmospheres and in interstellar and circumstellar environments. The aims of this Review are 3-fold: to highlight new photochemical insights enabled by the VUV-FEL at the DCLS, notably the recently recognized central atom elimination process that is shown to contribute in all of these triatomic molecules; to highlight some of the potential implications of this rich photochemistry to our understanding of interstellar chemistry and molecular evolution within the universe; and to highlight other and future research directions in areas related to chemical reaction dynamics and astrochemistry that will be enabled by increased access to VUV-FEL sources.

Vacuum ultraviolet photodissociation of sulfur dioxide and its implications for oxygen production in the early Earth's atmosphere.

The emergence of molecular oxygen (O2) in the Earth's primitive atmosphere is an issue of major interest. Although the biological processes leading to its accumulation in the Earth's atmosphere are well understood, its abiotic source is still not fully established. Here, we report a new direct dissociation channel yielding S(1D) + O2(a1Δg/X3Σg-) products from vacuum ultraviolet (VUV) photodissociation of SO2 in the wavelength range between 120 and 160 nm. Experimental results show O2 production to be an important channel from SO2 VUV photodissociation, with a branching ratio of 30 ± 5% at the H Lyman-α wavelength (121.6 nm). The relatively large amounts of SO2 emitted from volcanic eruptions in the Earth's late Archaean eon imply that VUV photodissociation of SO2 could have provided a crucial additional source term in the O2 budget in the Earth's primitive atmosphere. The results could also have implications for abiotic oxygen formation on other planets with atmospheres rich in volcanically outgassed SO2.

Molecular photodissociation dynamics revealed by Coulomb explosion imaging.

Coulomb explosion imaging (CEI) methods are finding ever-growing use as a means of exploring and distinguishing the static stereo-configurations of small quantum systems (molecules, clusters, etc). CEI experiments initiated by ultrafast (femtosecond-duration) laser pulses also allow opportunities to track the time-evolution of molecular structures, and thereby advance understanding of molecular fragmentation processes. This Perspective illustrates two emerging families of dynamical studies. 'One-colour' studies (employing strong field ionisation driven by intense near infrared or single X-ray or extreme ultraviolet laser pulses) afford routes to preparing multiply charged molecular cations and exploring how their fragmentation progresses from valence-dominated to Coulomb-dominated dynamics with increasing charge and how this evolution varies with molecular size and composition. 'Two-colour' studies use one ultrashort laser pulse to create electronically excited neutral molecules (or monocations), whose structural evolution is then probed as a function of pump-probe delay using an ultrafast ionisation pulse along with time and position-sensitive detection methods. This latter type of experiment has the potential to return new insights into not just molecular fragmentation processes but also charge transfer processes between moieties separating with much better defined stereochemical control than in contemporary ion-atom and ion-molecule charge transfer studies.