Product-pair Correlations Research Articles

High-resolution imaging of molecular collisions using a Zeeman decelerator.

We present the first crossed beam scattering experiment using a Zeeman decelerated molecular beam. The narrow velocity spreads of Zeeman decelerated NO (X2Π3/2, j = 3/2) radicals result in high-resolution scattering images, thereby fully resolving quantum diffraction oscillations in the angular scattering distribution for inelastic NO-Ne collisions and product-pair correlations in the radial scattering distribution for inelastic NO-O2 collisions. These measurements demonstrate similar resolution and sensitivity as in experiments using Stark decelerators, opening up possibilities for controlled and low-energy scattering experiments using chemically relevant species such as H and O atoms, O2 molecules, or NH radicals.

Real-time tracking of the entangled pathways in the multichannel photodissociation of acetaldehyde.

The roaming mechanism, an unconventional reaction path, was discovered more than a decade ago in the studies of formaldehyde photodissociation, H2CO → H2 + CO. Since then, observations of roaming have been claimed in numerous photochemical processes. A closer examination of the presented data, however, revealed that evidence for roaming is not always unequivocal, and some of the conclusions could be misleading. We report here an in-depth, joint experimental and theoretical study of the title reaction. By tracking the time-evolution of the pair-correlated product state distributions, we decipher the competing, interwoven reaction pathways that lead to the radical (CH3 + HCO) and molecular (CH4 + CO) products. Possible roaming pathways are then elucidated and a more precise descriptor of the phenomenon is delineated.

Direct observation of product-pair correlations in rotationally inelastic collisions of ND3 with D2.

We present a combined experimental and theoretical study of state-to-state inelastic scattering of ND3(j = 11-) with D2 (j = 0, 1, 2, 3) molecules at collision energies around 800 cm-1. Using a crossed molecular beam apparatus which employs the combination of Stark deceleration and velocity map imaging, we observe the correlated rotational excitations of both collision partners. For D2, both elastic (ΔjD2 = 0), inelastic excitation (j = 0 →j = 2) and inelastic de-excitation (j = 2 →j = 0) processes are observed. For a number of final ND3 states, inelastic channels in which D2 is rotationally excited or de-excited appear surprisingly strong. The experimental results are in excellent agreement with the predictions from quantum scattering calculations which are based on an ab initio ND3-D2 potential energy surface.

Observation of correlated excitations in bimolecular collisions.

Although collisions between atoms and molecules are largely understood, collisions between two molecules have proven much harder to study. In both experiment and theory, our ability to determine quantum-state-resolved bimolecular cross-sections lags behind their atom-molecule counterparts by decades. For many bimolecular systems, even rules of thumb-much less intuitive understanding-of scattering cross sections are lacking. Here, we report the measurement of state-to-state differential cross sections on the collision of state-selected and velocity-controlled nitric oxide (NO) radicals and oxygen (O2) molecules. Using velocity map imaging of the scattered NO radicals, the full product-pair correlations of rotational excitation that occurs in both collision partners from individual encounters are revealed. The correlated cross sections show surprisingly good agreement with quantum scattering calculations using ab initio NO-O2 potential energy surfaces. The observations show that the well-known energy-gap law that governs atom-molecule collisions does not generally apply to bimolecular excitation processes, and reveal a propensity rule for the vector correlation of product angular momenta.

Imaging the Effects of Bend-Excitation in the F + CD4(vb=0,1) → DF(v) + CD3(v2=1,2) Reactions

The title reaction was studied over the collisional energy range 0.9-4.0 kcal mol(-1), using a time-sliced velocity-imaging technique in a crossed-beam experiment. Both the integral and differential cross sections were measured in a product pair-correlation manner. Experimental evidence for the dual reaction mechanisms, a direct abstraction and a resonance-mediated pathway, were presented and await future theoretical confirmation.

Steric Effect in the Energy Transfer Reaction of Oriented CO (a 3Π, v′ = 0, Ω = 1 and 2) + NO (X 2Π) → NO (A 2Σ+, B 2Π) + CO (X 1Σ+)

The oriented CO (a (3)Π, v' = 0, Ω = 1 and 2) beam has been prepared by using an electric hexapole and applied to the energy transfer reaction of CO (a (3)Π, v' = 0, Ω = 1 and 2) + NO (X (2)Π) → NO (A (2)Σ(+), B (2)Π) + CO (X (1)Σ(+)). The emission spectra of NO (A (2)Σ(+), B(2)Π) have been measured at three orientation configurations (C-end, O-end, random). The shape of the emission spectra (and/or the internal excitation of products) turns out to be insensitive to the molecular orientation. The vibrational distributions of NO (A (2)Σ(+), v' = 0-2) and NO (B (2)Π, v' = 0-2) are determined to be N(v'=0):N(v'=1):N(v'=2) = 1:0.40 ± 0.05:0.10 ± 0.05 and N(v'=0):N(v'=1):N(v'= 2) = 1:0.6 ± 0.1:0.7 ± 0.1, respectively, and the branching ratio γ/β [=NO (A (2)Σ(+))/NO (B (2)Π)] is estimated to be γ/β ∼ 0.3 ± 0.1 by means of spectral simulation. These vibrational distributions of NO (A, B) can be essentially attributed to the product-pair correlations between CO (X, v″) and NO (A (2)Σ(+), v' = 0-2), NO (B (2)Π, v' = 0-2) due to energetic restriction under the vibrational distribution of CO (X, v″) produced from the vertical transition of CO (a (3)Π, v' = 0) → CO (X, v″) in the course of energy transfer. The steric opacity function has been determined at two wavelength regions: 220 < λ < 290 nm [NO (A → X) is dominant]; 320 < λ < 400 nm [NO (B → X) is dominant]. For both channels NO (A (2)Σ(+), B(2)Π), a significant CO (a (3)Π) alignment effect is recognized; the largest reactivity at the sideways direction with the small reactivity at the molecular axis direction is observed. These CO (a (3)Π) alignment effects can be essentially attributed to the steric asymmetry on two sets of molecular orbital overlap, [CO (2π) + NO (6σ (2π))] and [CO (5σ) + NO (1π (2π))]. All experimental observations support the electron exchange mechanism that is operative through the formation of a weakly bound complex OCNO.

Product pair correlation in bimolecular reactions

The vast majority of chemical reactions involve polyatomic species as reactants and/or products. The added degree of complexity offers opportunities to address dynamical questions other than those already encountered in a typical atom + diatom reaction. Product pair correlation is one of them. This article introduces the basic concept, outlines the experimental approach we developed and then highlights some of the applications to bimolecular reaction dynamics. Particular emphasis is placed on the information contents and unique insights gained from this type of measurements, which otherwise would have been lost by the conventional approach.

Rotationally selected product pair correlation: F+CD4→DF(ν′)+CD3(ν2=and2,N)

The product pair correlation of the title reaction was measured with rotational selection for both the vibrationally ground CD3(nu = 0) and umbrella-excited CD3(nu2 = 2) products. A striking linear relationship was found between the rotational energy of the selected CD3 product and the correlated kinetic energy release (or the average vibrational energy of the DF coproduct). Such a linearly correlated (or anticorrelated) dependence appears to be stronger for CD3(nu2 = 2,N) than for CD3(nu = 0,N). The mechanistic implication of the observation is that the rotational motion N of the CD3 product tends to lie antiparallel to the orbital angular momentum l' of the two departing products. The dependency on the K quantum number--the projection of N on the top axis--is, on the other hand, less significant yet noticeable.

Rotationally selected product pair correlation in F+CD(4)-->DF(nu('))+CD(3)(nu=0,N).

The title reaction was studied in a crossed-beam experiment by imaging of state-selected products. The rotational state selection of the CD(3) products was achieved using (2+1) resonance-enhanced multiphoton ionization. The coincident information on the DF coproducts was revealed in a state-resolved manner from time-sliced velocity map images. Significant dependences of both the correlated differential cross sections and the DF vibrational branching ratios on the "tagged" CD(3) rotation states were found. The dynamical implications of one of the major findings are discussed.

Insights into dynamics of the F+CD4 reaction via product pair correlation

To unravel the “extra-atom” complexity of the title reaction, we exploit an experimental approach which, by taking advantage of the correlated information of coincident product pairs, allows us to peel off judiciously the intrinsic complications of a six-atom reaction, extracting the underlying backbone of three-atom dynamics. Examining the collisional energy dependencies of the pair-correlated attributes for a given state(s) of CD3 products from the title reaction, several of major observations can qualitatively be understood, whereas others await further theoretical investigations. An intriguing possibility for the existence of reactive resonances in this six-atom reaction is surmised.

Doppler‐Resolved Laser Probing of Photon‐Initiated Bimolecular Collisions O(1D) + CH4 → OH(v,N) + CH3

AbstractThe stereodynamics of the reaction O(1D) + CH4 → OH(v ≤ 4,N) + CH3 at collision energies of ˜ 40 kJ mol−1, has been probed via Doppler‐resolved, polarized laser‐induced fluorescence spectroscopy. Velocity‐aligned, reagent O(1D) atoms were generated under bulb conditions via polarized laser photodissociation of N2O. Analysis of the Doppler profiles of nascent OH(v,N) fragments has allowed both scalar and vectorial product correlations to be determined, including differential scattering cross sections and rotational alignments. These imply the operation of a ‘delayed’ collision mechanism, dominated by the deeply attractive potential energy surface associated with the insertion to form CH3OH; the intermediacy of a long‐lived complex is excluded, however. Rotational angular momentum in the recoiling OH fragments is preferentially aligned perpendicular to, and azimuthally distributed about, their recoil velocity. The rotational excitation is thereby attributed to bending motion in the C···O···H plane during the reagent collisions. The scalar product pair correlations establish a near‐zero translational exoergicity and anticorrelated internal energy distributions in the two reaction products.