Multiphoton Ionization/Dissociation of Molecular Sulfur S2 in the UV Region.

The multiphoton ionization/dissociation dynamics of molecular sulfur (S2) in the ultraviolet range of 205-300 nm is studied using velocity map ion imaging (VMI). In this one-color experiment, molecular sulfur (S2) is generated in a pulsed discharge and then photodissociated by UV radiation. At the three-photon level, superexcited states are accessed via two different resonant states: the B3Σu- (v' = 8-11) valence states at the one-photon level and a Rydberg state at the two-photon level. Among the decay processes of these superexcited states, dissociation to electronically excited S atoms is dominant as compared to autoionization to ionic states S2+ (X2Πg) at wavelengths λ < 288 nm. The anisotropy parameter extracted from these images reflects the parallel character of these electronic transitions. In contrast, autoionization is found to be particularly efficient at S(1D) and S(1S) detection wavelengths around 288 nm. Information obtained from the kinetic energy distributions of S atoms has revealed the existence of vibrationally excited S2+ (X2Πg (v+ > 11)) that dissociates to ionic products following one-photon absorption. This work also reveals many interesting features of S2 photodynamics compared to those of electronically analogous O2.

Vibrational state-specific nonadiabatic photodissociation dynamics of OCS+ via A2Π1/2 (ν1 0 ν3) states.

The identification and analysis of quantum state-specific effects can significantly deepen our understanding of detailed photodissociation dynamics. Here, we report an experimental investigation on the vibrational state-mediated photodissociation of the OCS+ cation via the A2Π1/2 (ν1 0 ν3) states by using the velocity map ion imaging technique over the photolysis wavelength range of 263-294 nm. It was found that the electronically excited S+ product channel S+(2Du) + CO (X1Σ+) was significantly enhanced when the ν1 and ν3 vibrational modes were excited. Clear deviations in the branching ratios of the electronically excited S+ channel were observed when the vibrational modes ν1 and ν3 were selectively excited. The results reveal that vibrationally excited states play a vital role in influencing the nonadiabatic couplings in the photodissociation process.

Imaging rotational energy transfer: comparative stereodynamics in CO + N2 and CO + CO inelastic scattering.

State-to-state rotational energy transfer in collisions of ground ro-vibrational state 13CO molecules with N2 molecules has been studied using the crossed molecular beam method under kinematically equivalent conditions used for 13CO + CO rotationally inelastic scattering described in a previously published report (Sun et al., Science, 2020, 369, 307-309). The collisionally excited 13CO molecule products are detected by the same (1 + 1' + 1'') VUV (Vacuum Ultra-Violet) resonance enhanced multiphoton ionization scheme coupled with velocity map ion imaging. We present differential cross sections and scattering angle resolved rotational angular momentum alignment moments extracted from experimentally measured 13CO + N2 scattering images and compare them with theoretical predictions from quasi-classical trajectories (QCT) on a newly calculated 13CO-N2 potential energy surface (PES). Good agreement between experiment and theory is found, which confirms the accuracy of the 13CO-N2 potential energy surface for the 1460 cm-1 collision energy studied by experiment. Experimental results for 13CO + N2 are compared with those for 13CO + CO collisions. The angle-resolved product rotational angular momentum alignment moments for the two scattering systems are very similar, which indicates that the collision induced alignment dynamics observed for both systems are dominated by a hard-shell nature. However, compared to the 13CO + CO measurements, the primary rainbow maximum in the DCSs for 13CO + N2 is peaked consistently at more backward scattering angles and the secondary maximum becomes much less obvious, implying that the 13CO-N2 PES is less anisotropic. In addition, a forward scattering component with high rotational excitation seen for 13CO + CO does not appear for 13CO-N2 in the experiment and is not predicted by QCT theory. Some of these differences in collision dynamics behaviour can be predicted by a comparison between the properties of the PESs for the two systems. More specific behaviour is also predicted from analysis of the dependence on the relative collision geometry of 13CO + N2 trajectories compared to 13CO + CO trajectories, which shows the special 'do-si-do' pathway invoked for 13CO + CO is not effective for 13CO + N2 collisions.

Disentangling Multiphoton Ionization and Dissociation Channels in Molecular Oxygen Using Photoelectron-Photoion Coincidence Imaging.

Multiphoton excitation of molecular oxygen in the 392-408 nm region is studied using a tunable femtosecond laser coupled with a double velocity map imaging photoelectron-photoion coincidence spectrometer. The laser intensity is held at ≤∼1 TW/cm2 to ensure excitation in the perturbative regime, where the possibility of resonance enhanced multiphoton ionization (REMPI) can be investigated. O2+ production is found to be resonance enhanced around 400 nm via three-photon excitation to the e'3Δu(v = 0) state, similar to results from REMPI studies using nanosecond dye lasers. O+ production reaches 7% of the total ion yield around 405 nm due to two processes: autoionization following five-photon excitation of O2, producing O2+(X(v)) in a wide range of vibrational states followed by two- or three-photon dissociation, or six-photon excitation to a superexcited O2** state followed by neutral dissociation and subsequent ionization of the electronically excited O atom. Coincidence detection is shown to be crucial in identifying these competing pathways.

Vacuum ultraviolet photodissociation dynamics of OCS via the F Rydberg state: The O (3PJ=2,1,0) product channels.

We study the vacuum ultraviolet (VUV) photodissociation dynamics of carbonyl sulfide (OCS) by using the time sliced velocity map ion imaging technique. Experimental images of the dissociative O (3PJ=0,1,2) products were acquired at five VUV photolysis wavelengths from 133.26 to 139.96 nm that correspond to the F Rydberg state of OCS. High vibrational states of the carbon monosulfide (CS) co-products are partially resolved in the images. The product total kinetic energy releases, angular distributions, and the product state branching ratios were derived from the experimental images. Notably, it is found that the anisotropic parameters change systematically with the photolysis wavelength. The anisotropic parameters and the product state branching ratios are significantly sensitive to the J quantum number of the O (3PJ) products. The phenomenon indicates that multiple nonadiabatic pathways are strongly involved in the photodissociation processes.

Dynamics and vector correlations of vacuum ultraviolet (VUV) photodissociation of CO2 at 155 nm.

In this work, the CO2 Vacuum Ultraviolet (VUV) photodissociation dynamics of the dominant O(1D) channel near 155 nm have been studied using Velocity Map Imaging (VMI) technique. Correlations among the transition dipole moment of the parent molecule, recoil velocity vector and rotational angular momentum vector of the photofragments were extracted from the anisotropic angular distributions of the images. The vector correlations extracted indicated a picture of photodissociation mainly via the excited 21A' (A) state. The transition dipole moment  lies in the bending molecular plane, and the j⃑ is pointing perpendicular to the plane, while the µ-v vectors angle is between 41°-45°. In addition, a clear trend was observed. As the product CO rotational state j increases, the spatial anisotropy parameter (ß ≡ 2ß20(20)) decreases. This j-dependent attenuation of spatial anisotropy parameter can be explained mainly with the consideration of non-axial recoil effect. These results are in good agreement with both theoretical work and previous experimental work.

State-to-state photodissociation dynamics of CO2 at 157 nm.

State-to-state photodissociation of CO2(v2 = 0 and 1) at 157 nm via the O(1D) + CO(X1Σ+) channel was studied by using the sliced velocity map imaging technique. Both the O(1D) and CO(X1Σ+) products were detected by (2 + 1) resonance enhanced multiphoton ionization (REMPI). Detection of CO via the B1Σ+ ←← X1Σ+ transition allowed ro-vibrational state-selective detection, and combined with imaging, the fragment energy and angular distributions have been derived. For CO(v = 0 and 1|j) products from the CO2(v2 = 0) molecule, the angular distributions of low-j CO display positive anisotropic parameters (about 0.8); with j increasing, the product anisotropic parameters gradually reduce to zero. While for CO(v = 0 and 1|j) products from the vibrational excited CO2(v2 = 1) molecule, the angular distributions of low-j CO also display positive anisotropic parameters; with j increasing, the product anisotropic parameters first decrease to zero and then become negative (about -0.5). Experimental results show that the observed variation of the product angular distribution with the rotational quantum number of CO is consistent with trends predicted by a classical model for non-axial fragment recoil. The results support advanced theoretical predictions of a predominantly parallel transition to the bent 21A' excited state of CO2, where bending introduces torque during the direct dissociation process.

Photodissociation Dynamics of Astrophysically Relevant Propyl Derivatives (C3H7X; X = CN, OH, HCO) at 157 nm Exploiting an Ultracompact Velocity Map Imaging Spectrometer: The (Iso)Propyl Channel.

The photodissociation dynamics of astrophysically relevant propyl derivatives (C3H7X; X = CN, OH, HCO) at 157 nm exploiting an ultracompact velocity map imaging (UVMIS) setup has been reported. The successful operation of UVMIS allowed the exploration of the 157 nm photodissociation of six (iso)propyl systems─n/i-propyl cyanide (C3H7CN), n/i-propyl alcohol (C3H7OH), and (iso)butanal (C3H7CHO)─to explore the C3H7 loss channel. The distinct center-of-mass translational energy distributions for the i-C3H7X (X= CN, OH, HCO) could be explained through preferential excitation of the low frequency C-H bending modes of the formyl moiety compared to the higher frequency stretching of the cyano and hydroxy moieties. Although the ionization energy of the n-C3H7 radical exceeds the energy of a 157 nm photon, C3H7+ was observed in the n-C3H7X (X = CN, OH, HCO) systems as a result of photoionization of vibrationally "hot" n-C3H7 fragments, photoionization of i-C3H7 after a hydrogen shift in vibrationally "hot" n-C3H7 radicals, and/or two-photon ionization. Our experiments reveal that at least the isopropyl radical (i-C3H7) and possibly the normal propyl radical (n-C3H7) should be present in the interstellar medium and hence searched for by radio telescopes.

Femtosecond 2 + 1 Resonance-Enhanced Multiphoton Ionization Spectroscopy of the C-State in Molecular Oxygen.

Coincidence electron-cation imaging is used to characterize the multiphoton ionization of O2 via the v = 4,5 levels of the 3s(3Πg) Rydberg state. A tunable 100 fs laser beam operating in the 271-263 nm region is found to cause a nonresonant ionization across this wavelength range, with an additional resonant ionization channel only observed when tuned to the 3Πg(v = 5) level. A distinct 3s → p wave character is observed in the photoelectron angular distribution for the v = 5 channel when on resonance.

Detection of the O2 A'3ΔU Herzberg III state by photofragment imaging.

Photofragment imaging is shown to provide a sensitive method for detection of the O2 A'3Δu Herzberg III state using a one-laser dissociation/O(1D) resonance enhanced multiphoton ionization (REMPI) scheme with a focused nanosecond dye laser beam tuned to 203.8 or 205.2 nm, combined with velocity map imaging of the atomic oxygen photofragment. O2 populated in the Herzberg states is generated by photodesorption at 250 nm of solid O2 ice held at 15 K and by an electric discharge in a pulsed molecular beam of pure O2. Ice photo-desorption results in Herzberg state products with higher translational, vibrational and rotational energy spreads, yielding the same signal as the discharge source but with lower velocity resolution. A clear signal with parallel character (ß âˆ¼ 0.9) assigned to dissociation of O2 A'3Δu(v = 0, 1 Ω = 1) was observed when using a pulsed electric discharge source under specific 'cold' conditions with O(1D) detection, driving one-photon dissociation around 205 nm. No products corresponding to O2 A'3Δu state dissociation were observed for 225.625 or 200.32 nm dissociation with O(3P2) detection, which implies that the O2 A'3Δu state dissociates exclusively to the third (O1D + O1D) dissociation limit. Dissociation is suggested to take place through the 21Πg upper state to the O1D + O1D limit where spin-orbit coupling of the A'3Δu state with the 11Πu state accesses the allowed parallel 1Πu → 1Πg transition. While the absence of a parallel-type photodissociation signal from the c1Σ-u state may be expected, the A3Σ+u should spin-orbit couple through the same pathway as the A'3Δu state. The fact that no clear A3Σ+u signal is observed suggests a faster deactivation process compared to the A'3Δu state in the discharge and ice desorption process.

Collision-induced absorption between O2-CO2 for the a1Δg (v = 1) ← X3Σ (v = 0) transition of molecular oxygen at 1060 nm.

Collision-induced absorption between O2 and CO2 molecules associated with the a1Δg (v = 1) ← X3Σ-g (v = 0) band of oxygen around 1060 nm was measured using cavity ring-down spectroscopy. The lineshape for this transition is measured for the first time, and the integrated cross-section is found to be smaller than the only previous report. For pure oxygen, we find an integrated absorption value of (2.10 ± 0.31) × 10-4 cm-2 amg-2 which is in good agreement with the previous reported values. For O2-CO2 collisions we report an integrated value of (6.37 ± 1.09) × 10-5 cm-2 amg-2 which is small but still significant and not accounted for by theory.

Imaging inelastic scattering of CO with argon: polarization dependent differential cross sections.

Rotationally inelastic scattering of carbon monoxide (CO) with Argon at a collision energy of 700 cm-1 has been investigated by measuring polarization dependent differential scattering cross sections (PDDCSs) for rotationally excited CO molecules using a crossed molecular beam apparatus coupled with velocity-map ion imaging. A simple and robust (1 + 1' + 1'') VUV (Vacuum Ultra-Violet) REMPI (Resonance Enhanced Multi Photon Ionization) scheme is used and images are obtained by setting the VUV light polarization direction parallel or perpendicular to the scattering plane. Clear differences between the images for the two polarizations are observed, indicating strong collision induced alignment of the rotational angular momentum of scattered CO. A direct image analysis procedure as described in our previously published paper (A. G. Suits et al., J. Phys. Chem. A., 2015, 119, 5925), is employed to extract the fully quantum state resolved alignment-free differential cross sections (DCSs) and the state-to-state angle-dependent alignment moments for each final rotational state. The experimental results are compared with advanced theory, in particular with the predictions of CC QM (Close-Coupling Quantum Mechanical) and QCT (Quasi-Classical Trajectory) calculations. The agreement between experiment and theory is generally found to be quite good throughout the entire scattering angle range for all the final states probed, showing the reliability of the experiment and use of the direct extraction method, as well as the accuracy of the potential surface over the studied collision energy range. A classical kinematic apse (hard shell) model was found to be useful in interpreting the measured collision induced alignment moments.

Communication: State-to-state inelastic scattering of interstellar O2 with H2.

Molecular oxygen (O2) is predicted to be a major reservoir of elemental oxygen in dense interstellar molecular clouds. However, the abundance of O2 derived from astronomical observations is much lower than expected. Solving the discrepancies between models and observations requires a review of the chemistry and collisional excitation of O2 in space. In particular, O2-H2 collisions are crucial to derive O2 abundance in space from the interstellar spectra. A crossed molecular beam experiment to probe the rotational excitation of O2 due to H2 collisions at energies of 650 cm-1 is reported. Velocity map imaging was combined with state-selective detection of O2( X 3 Σ g - ) by (2 + 1) resonance-enhanced multiphoton ionization. The obtained raw O 2 + images were corrected from density to flux and the differential cross sections (DCSs) were then extracted. Exact quantum mechanical calculations were also performed. Very good agreement between experimental and theoretical DCSs was found. The agreement demonstrates our ability to determine inelastic processes between O2 molecules and H2 both theoretically and experimentally and that the excitation of O2 in the interstellar medium can be correctly modeled. Consequences on the astrophysical modeling are briefly evaluated.

Perspective: Advanced particle imaging.

Since the first ion imaging experiment [D. W. Chandler and P. L. Houston, J. Chem. Phys. 87, 1445-1447 (1987)], demonstrating the capability of collecting an image of the photofragments from a unimolecular dissociation event and analyzing that image to obtain the three-dimensional velocity distribution of the fragments, the efficacy and breadth of application of the ion imaging technique have continued to improve and grow. With the addition of velocity mapping, ion/electron centroiding, and slice imaging techniques, the versatility and velocity resolution have been unmatched. Recent improvements in molecular beam, laser, sensor, and computer technology are allowing even more advanced particle imaging experiments, and eventually we can expect multi-mass imaging with co-variance and full coincidence capability on a single shot basis with repetition rates in the kilohertz range. This progress should further enable "complete" experiments-the holy grail of molecular dynamics-where all quantum numbers of reactants and products of a bimolecular scattering event are fully determined and even under our control.

Imaging state-to-state reactive scattering in the Ar+ + H2 charge transfer reaction.

The charge transfer reaction of Ar+ with H2 and D2 has been investigated in an experiment combining crossed beams with three-dimensional velocity map imaging. Angle-differential cross sections for two collision energies have been obtained for both neutral species. We find that the product ions are highly internally excited. In the reaction with H2, the spin-orbit excited Ar+ state's coupling to the "resonant" vibrationally excited product H2+ (υ = 2) dominates for both investigated energies, in line with previous investigations. The observed angular distributions, however, show significantly less back-scattering than was found previously. Furthermore, we discovered that the product ions are highly rotationally excited. In the case of Ar+ reacting with D2, the energetically closest lying vibrational levels are not strictly preferred and higher-lying vibrational levels are also populated. For both species, the backward-scattered products show higher internal excitation.

State-to-State Inelastic Scattering of O2 with Helium.

Molecular oxygen (O2) is extremely important for a wide variety of processes on and outside Earth. Indeed, O2­He collisions are crucial to model O2 abundance in space or to create ultracold O2 molecules. A crossed molecular beam experiment to probe rotational excitation of O2 due to helium collisions at energies of 660 cm­1 is reported. Velocity map imaging was combined with state-selective detection of O2(X3Σg­) by (2+1) resonance-enhanced multiphoton ionization. The obtained raw O2+ images were corrected from density to flux and the differential cross sections (DCS) were then extracted for six O2 final states. Exact quantum mechanical calculations were also performed. A very good agreement between experimental and theoretical DCSs was found by using an initial O2 beam population ratio of 80% for the first rotational state and 20% for the first excited state. The agreement demonstrates our ability to model inelastic processes between O2 molecules and rare gas both theoretically and experimentally.

Singlet oxygen photogeneration from X-O2 van der Waals complexes: double spin-flip vs. charge-transfer mechanism.

The channel of singlet oxygen O2((1)Δg) photogeneration from van der Waals complexes of oxygen X-O2 has been investigated to discriminate between two possible mechanisms based on charge-transfer (CT) or double spin-flip (DSF) transitions. The results obtained in this work for complexes with X = ethylene C2H4, 1,3-butadiene C4H6, deuterated methyl iodide CD3I, benzene C6H6 and water H2O and for those investigated previously indicate the DSF mechanism as a source of singlet oxygen. The formation of O2((1)Δg) is observed only when the energy of exciting quantum is sufficient for DSF transition. Universally detected low vibrational excitation of O2((1)Δg) arising in the photodissociation of van der Waals complexes X-O2 indicates the DSF mechanism as its source. For complex of ethylene C2H4-O2ab initio calculations of vertical energy ΔE(vert) for DSF and CT transitions have been carried out. The positive results of singlet oxygen formation from C2H4-O2 can be explained by the DSF but not by the CT mechanism.

The Jahn-Teller effect in the presence of partial isotopic substitution: the B̃(1)E'' state of NH2D and NHD2.

Rotationally resolved resonance enhanced multiphoton ionisation spectra of the B̃(1)E'' state of NH2D are presented and analysed. The analysis indicates a small (34.9 cm(-1)) lifting of the vibronic degeneracy of the zero point level, approximately equal in sign but opposite in magnitude to the splitting observed in NHD2 in previous work. This observation is consistent with previous measurements on systems with partial isotopic substitution subject to a mild Jahn-Teller effect. A model is developed to calculate the splitting induced by asymmetric isotopic substitution of a degenerate electronic state, based on a harmonic force field with linear and quadratic Jahn-Teller terms added. The force field is developed in internal co-ordinates to allow the same parameters to be used to calculate the pattern of vibronic levels for all four isotopologues. The lifting of the degeneracy of the zero point level on asymmetric substitution comes from the quadratic Jahn-Teller effect; the linear term does not lift the degeneracy.

Direct Extraction of Alignment Moments from Inelastic Scattering Images.

We present a novel means of analyzing velocity-map images of angular momentum polarization in inelastic scattering. In this approach, linear combinations of angular distributions obtained by integrating select regions of images for two probe laser polarizations directly yield the alignment-free differential cross sections and the differential alignment moments. No fitting is needed in the analysis. The method relies on the fact that the angular distribution for out-of-plane scattering is encoded in the distribution along the relative velocity vector, and this may be recovered quantitatively owing to the redundancy of the in-plane and out-of-plane scattering for the horizontal polarization case.

Rotationally Inelastic Scattering of Quantum-State-Selected ND3 with Ar.

Rotationally inelastic scattering of ND3 with Ar is studied at mean collision energies of 410 and 310 cm(­1). In the experimental component of the study, ND3 molecules are prepared by supersonic expansion and subsequent hexapole state selection in the ground electronic and vibrational levels and in the jk(±) = 1(1) rotational level. A beam of state-selected ND3 molecules is crossed with a beam of Ar, and scattered ND3 molecules are detected in single final j'k'(±) quantum states using resonance enhanced multiphoton ionization spectroscopy. State-to-state differential cross sections for rotational-level changing collisions are obtained by velocity map imaging. The experimental measurements are compared with close-coupling quantum-mechanical scattering calculations performed using an ab initio potential energy surface. The computed DCSs agree well with the experimental measurements, confirming the high quality of the potential energy surface. The angular distributions are dominated by forward scattering for all measured final rotational and vibrational inversion symmetry states. This outcome is in contrast to our recent results for inelastic scattering of ND3 with He, where we observed significant amount of sideways and backward scattering for some final rotational levels of ND3. The differences between He and Ar collision partners are explained by differences in the potential energy surfaces that govern the scattering dynamics.