Cunshun Huang

State-resolved reactive scattering by slice imaging: A new view of the Cl+C2H6 reaction

We present state-resolved crossed beam scattering results for the reaction Cl+C2H6-->HCl+C2H5, obtained using direct current slice imaging. The HCl (v=0,J=2) image, recorded at a collision energy of 6.7+/-0.6 kcalmol, shows strongly coupled angular and translational energy distributions revealing features of the reaction not seen in previous studies. The overall distribution is mainly forward scattered with respect to the Cl beam, with a translational energy distribution peaking near the collision energy. However, there is a substantial backscattered contribution that is very different. It shows a sharp peak at 8.0 kcalmol, but extends to much lower energy, implying substantial internal excitation in the ethyl radical coproduct. These results provide new insight into the reaction, and they are considered in terms of alternative models of the dynamics. This work represents the first genuine crossed-beam study in which a product other than the methyl radical was detected with quantum state specificity, showing the promise of the approach generally for high resolution state-resolved reactive scattering.

Rotationally resolved reactive scattering: Imaging detailed Cl+C2H6 reaction dynamics

The hydrogen atom abstraction reaction of Cl (2P3/2) with ethane has been studied using the crossed molecular beam technique with dc slice imaging at collision energies from 3.2 to 10.4 kcal/mol. The products HCl (v,J) (v = 0, J = 0-5) were state-selectively detected using 2+1 resonance enhanced multiphoton ionization. The images were used to obtain the center-of-mass frame product angular distributions and translational energy release distributions. Two general features were found in all probed HCl quantum states at 6.7 kcal/mol collision energy, and these features have distinct translational energy release and angular distributions, as described for HCl (v = 0, J = 2) in a recent preliminary report [Li et al., J. Chem. Phys. 124, 011102 (2006)]. The results for HCl (v = 0, J = 2) at four collision energies were also compared to investigate the energy-dependent dynamics. We discuss the reaction in terms of a variety of models of polyatomic reaction dynamics. The dynamics of this well studied system are more complicated than can be accounted for by a single mechanism, and the results call for further theoretical and experimental investigations.

Dynamics of CN+alkane reactions by crossed-beam dc slice imaging

The hydrogen atom abstraction reactions of CN (X (2)Sigma(+)) with alkanes have been studied using the crossed molecular beam technique with dc slice ion imaging at collision energies of 7.5 and 10.8 kcalmol. The product alkyl radical images were obtained via single photon ionization at 157 nm for the reactions of CN (X (2)Sigma(+)) with n-butane, n-pentane, n-hexane, and cyclohexane. From analysis of the images, we obtained the center-of-mass frame product angular distributions and translational energy distributions directly. The results indicate that the products are largely backscattered and that most of the available energy ( approximately 80%-85%) goes to the internal energy of the products. The reaction dynamics is discussed in light of recent kinetics data, theoretical calculations, and results for related halogen and oxygen atom reactions.

H elimination and metastable lifetimes in the UV photoexcitation of diacetylene

We present an experimental investigation of the UV photochemistry of diacetylene under collisionless conditions. The H loss channel is studied using DC slice ion imaging with two-color reduced-Doppler detection at 243 nm and 212 nm. The photochemistry is further studied deep in the vacuum UV, that is, at Lyman-alpha (121.6 nm). Translational energy distributions for the H + C4H product arising from dissociation of C4H2 after excitation at 243, 212, and 121.6 nm show an isotropic angular distribution and characteristic translational energy profile suggesting statistical dissociation from the ground state or possibly from a low-lying triplet state. From these distributions, a two-photon dissociation process is inferred at 243 nm and 212 nm, whereas at 121.6 nm, a one-photon dissociation process prevails. The results are interpreted with the aid of ab initio calculations on the reaction pathways and statistical calculations of the dissociation rates and product branching. In a second series of experiments, nanosecond time-resolved phototionization measurements yield a direct determination of the lifetime of metastable triplet diacetylene under collisionless conditions, as well as its dependence on excitation energy. The observed submicrosecond lifetimes suggest that reactions of metastable diacetylene are likely to be less important in Titans atmosphere than previously believed.

Two-color reduced-Doppler ion imaging

We demonstrate a two-color reduced-Doppler probe for ion imaging that, in many applications, offers advantages over conventional 2+1 resonance-enhanced multiphoton ionization detection. Using counterpropagating beams of two different colors, one of which is broadband 266 nm, we achieve convenient and sensitive D atom detection without the need for Doppler scanning. We demonstrate the approach using 224 nm photodissociation of DBr. This method improves the sensitivity and signal-to-noise ratio and presents advantages and opportunities for use in the other systems.

State-selected imaging studies of formic acid photodissociation dynamics

The photodissociation dynamics of formic acid have been studied using the velocity map ion imaging at the UV region. The measurements were made with resonance enhancement multiphoton ionization (REMPI) spectroscopy and dc slicing ion imaging. The OH REMPI spectrum from the photodissociation of formic acid at 244 nm has been recorded. The spectrum shows low rotational excitation (N<or=4). By fixing the probe laser at the specific rotational transitions, the resulting OH images from various dissociation wavelengths have been accumulated. The translational energy distributions derived from the OH images imply that about half of the available energies go to the photofragments internal excitation. The dissociation dynamics of formic acid were also discussed in view of the recent theoretical calculations.

[1 + 1] photodissociation of CS2+(X̃2Πg) via the vibrationally mediated B̃2Σu+ state: Multichannels exhibiting and mode specific dynamics

Dissociation dynamics of CS(2)(+) vibrationally mediated via its B̃(2)Σ(u)(+) state, was studied using the time-sliced velocity map imaging technique. The parent CS(2)(+) cation was prepared in its X̃(2)Π(g) ground state through a [3 + 1] resonance enhanced multiphoton ionization process, via the 4pσ(3)Π(u) intermediate Rydberg state of neutral CS(2) molecule at 483.14 nm. CS(2)(+)(X̃(2)Π(g)) was dissociated by a [1 + 1] photoexcitation mediated via the vibrationally selected B̃ state over a wavelength range of 267-283 nm. At these wavelengths the C̃(2)Σ(g)(+) and D̃(2)Σ(u)(+) states are excited, followed by numerous S(+) and CS(+) dissociation channels. The S(+) channels specified as three distinct regions were shown with vibrationally resolved structures, in contrast to the less-resolved structures being presented in the CS(+) channels. The average translational energy releases were obtained, and the S(+)∕CS(+) branching ratios with mode specificity were measured. Two types of dissociation mechanisms are proposed. One mechanism is the direct coupling of the C̃ and D̃ states with the repulsive satellite states leading to the fast photofragmentation. The other mechanism is the internal conversion of the C̃ and D̃ states to the B̃ state, followed by the slow fragmentation occurred via the coupling with the repulsive satellite states.

PHOTODISSOCIATION OF THE DIACETYLENE DIMER AND IMPLICATIONS FOR HYDROCARBON GROWTH IN TITAN'S ATMOSPHERE

The surface of Titan is obscured by multiple aerosol layers whose composition and formation mechanism have remained poorly understood. These organic haze layers are believed to arise from photolysis and electron impact triggered chemistry in the dense nitrogen (N2) and methane (CH4) atmosphere involving highly unsaturated hydrocarbon molecules such as acetylene (HCCH), diacetylene (HCCCCH), and triacetylene (HCCCCCCH). Here we show via laboratory studies combined with electronic structure calculations that the photodissociation of the diacetylene dimer ((HCCCCH)2) readily initiates atomic hydrogen loss and atomic hydrogen transfer reactions forming two prototypes of resonantly stabilized free radicals, C4H3 and C8H3, respectively. These structures represent hydrogenated polyynes which can neither be synthesized via traditional photodissociation pathways of the monomer nor via hydrogen addition to the polyynes. The photodissociation dynamics of mixed dimers involving acetylene, diacetylene, and even triacetylene present a novel, hitherto overlooked reaction class and show the potential to synthesize more complex, resonantly stabilized free radicals considered to be major building blocks to polycyclic aromatic hydrocarbons in Titans low-temperature atmosphere.

Imaging the pair-correlated hnco photodissociation: The nh(a(1)delta) + co(x-1 sigma(+)) channel

The NH(a(1)Δ) + CO(X(1)Σ(+)) product channel for the photodissociation of HNCO at 201 nm was investigated using the sliced velocity map ion imaging technique with the detection of NH(a(1)Δ) products via (2 + 1) resonance enhanced multiphoton ionization (REMPI). Images were measured for the NH(a(1)Δ) rotational states in the ground and vibrational excited states (v = 0 and 1). Correlation between the NH(a(1)Δ) and CO rovibrational state distributions were determined from these images. Experimental results show that the vibrational distribution of the CO fragment in the NH(a(1)Δ) + CO(X(1)Σ(+)) channel peaks at v = 1. The negative anisotropy parameter measured for the NH(a(1)Δ) (v = 0 and 1|j) products indicates a direct dissociation process for the N-C bond cleavage in the S1 state. A bimodal CO rotational distribution was observed, suggesting that HNCO dissociates in the S1 state in two distinctive pathways.

State-selected imaging of HCCO radical photodissociation dynamics

We present a dc sliced ion imaging study of HCCO radical photodissociation to CH and CO at 230 nm. The measurements were made using a two-color reduced Doppler probe strategy. The CO rotational distribution was consistent with a Boltzmann distribution at 3500 K. Using the dc slice ion imaging approach, we obtained CO images for various rotational levels of CO (v=0). The results are largely consistent with earlier work, albeit with a significant 0.9 eV peak seen previously in the translational energy distributions absent in our state-selected imaging study.