Eckart Wrede

Experimental determination of quantum state resolved differential cross sections for the hydrogen exchange reaction H+D2→HD+D

We have carried out a systematic crossed molecular beam study of the hydrogen exchange reaction in the H+D2→HD+D isotopic form at two collision energies: 0.53 and 1.28 eV. The Rydberg atom time-of-flight method was used to measure the D-atom product angle-velocity distribution. For the first time ro-vibrational quantum state resolved differential cross sections for the title reaction were measured, which can directly be compared to theoretical predictions at this detailed level. Experimental results are compared to theoretical predictions from both quasi classical and quantum mechanical calculations on different potential energy surfaces as well as to earlier experiments. A general good agreement is found for the converged quantum mechanical calculations with indications that the Boothroyd-Keogh-Martin-Peterson potential energy surface is better suited to describe the dynamics of the reaction. For the higher collision energy the quasi classical trajectory calculations reproduce the experimental data quite...

Observation and interpretation of a time-delayed mechanism in the hydrogen exchange reaction

Extensive theoretical and experimental studies have shown the hydrogen exchange reaction H + H2 → H2 + H to occur predominantly through a ‘direct recoil’ mechanism: the H–H bonds break and form concertedly while the system passes straight over a collinear transition state, with recoil from the collision causing the H2 product molecules to scatter backward. Theoretical predictions agree well with experimental observations of this scattering process. Indirect exchange mechanisms involving H3 intermediates have been suggested to occur as well, but these are difficult to test because bimolecular reactions cannot be studied by the femtosecond spectroscopies used to monitor unimolecular reactions. Moreover, full quantum simulations of the time evolution of bimolecular reactions have not been performed. For the isotopic variant of the hydrogen exchange reaction, H + D2 → HD + D, forward scattering features observed in the product angular distribution have been attributed to possible scattering resonances associated with a quasibound collision complex. Here we extend these measurements to a wide range of collision energies and interpret the results using a full time-dependent quantum simulation of the reaction, thus showing that two different reaction mechanisms modulate the measured product angular distribution features. One of the mechanisms is direct and leads to backward scattering, the other is indirect and leads to forward scattering after a delay of about 25 femtoseconds.

Toward real-time charged-particle image reconstruction using polar onion-peeling.

A method to reconstruct full three-dimensional photofragment distributions from their two-dimensional (2D) projection onto a detection plane is presented, for processes in which the expanding Newton sphere has cylindrical symmetry around an axis parallel to the projection plane. The method is based on: (1) onion-peeling in polar coordinates [Zhao et al., Rev. Sci. Instrum. 73, 3044 (2002)] in which the contribution to the 2D projection from events outside the plane bisecting the Newton sphere are subtracted in polar coordinates at incrementally decreasing radii; and (2) ideas borrowed from the basis set expansion (pBASEX) method in polar coordinates [Garcia et al., Rev. Sci. Instrum. 75, 4989 (2004)], which we use to generate 2D projections at each incremental radius for the subtraction. Our method is as good as the pBASEX method in terms of accuracy, is devoid of centerline noise common to reconstruction methods employing Cartesian coordinates; and it is computationally cheap allowing images to be reconstructed as they are being acquired in a typical imaging experiment.

Experimental Studies and Theoretical Predictions for the H + D2 → > HD + D Reaction

The H + H2 exchange reaction constitutes an excellent benchmark with which to test dynamical theories against experiments. The H + D2 (vibrational quantum number v = 0, rotational quantum number j = 0) reaction has been studied in crossed molecular beams at a collision energy of 1.28 electron volts, with the use of the technique of Rydberg atom time-of-flight spectroscopy. The experimental resolution achieved permits the determination of fully rovibrational state-resolved differential cross sections. The high-resolution data allow a detailed assessment of the applicability and quality of quasi-classical trajectory (QCT) and quantum mechanical (QM) calculations. The experimental results are in excellent agreement with the QM results and in slightly worse agreement with the QCT results. This theoretical reproduction of the experimental data was achieved without explicit consideration of geometric phase effects.

Continuum state spectroscopy: A high resolution ion imaging study of IBr photolysis in the wavelength range 440–685 nm

The photodissociation of jet-cooled IBr molecules has been investigated at numerous excitation wavelengths in the range 440–685 nm using a state-of-art ion imaging spectrometer operating under optimal conditions for velocity mapping. Image analysis provides precise threshold energies for the ground, I(2P3/2)+Br(2P3/2), and first excited [I(2P3/2)+Br(2P1/2)] dissociation asymptotes, the electronic branching into these two active product channels, and the recoil anisotropy of each set of products, as a function of excitation wavelength. Such experimental data have allowed mapping of the partial cross-sections for parallel (i.e., ΔΩ=0) and perpendicular (i.e., ΔΩ=±1) absorptions and thus deconvolution of the separately measured (room temperature) parent absorption spectrum into contributions associated with excitation to the A 3Π(1), B 3Π(0+) and 1Π(1) excited states of IBr. Such analyses of the continuous absorption spectrum of IBr, taken together with previous spectroscopic data for the bound levels suppor...

The dynamics of the hydrogen exchange reaction at 2.20 eV collision energy: Comparison of experimental and theoretical differential cross sections

The H+D2(v=0,j=0)→HD(v′,j′)+D isotopic variant of the hydrogen atom exchange reaction has been studied in a crossed molecular beam experiment at a collision energy of 2.20 eV. Kinetic energy spectra of the nascent D atoms were obtained by using the Rydberg atom time-of-flight technique. The extensive set of spectra collected has permitted the derivation of rovibrationally state-resolved differential cross sections in the center-of-mass frame for most of the internal states of the HD product molecules, allowing a direct comparison with theoretical predictions. Accurate 3D quantum mechanical calculations have been carried out on the refined version of the latest Boothroyd–Keogh–Martin–Peterson potential energy surface, yielding an excellent agreement with the experimentally determined differential cross sections. The comparison of the results from quasi-classical trajectory calculations on the same potential surface reveals some discrepancies with the measured data, but shows a good global accordance. The t...

On the dynamics of the H(+) + D2(v=0, j=0) --> HD + D(+) reaction: A comparison between theory and experiment

The H+ +D2(v=0,j=0)-->HD+D + reaction has been theoretically investigated by means of a time independent exact quantum mechanical approach, a quantum wave packet calculation within an adiabatic centrifugal sudden approximation, a statistical quantum model, and a quasiclassical trajectory calculation. Besides reaction probabilities as a function of collision energy at different values of the total angular momentum, J, special emphasis has been made at two specific collision energies, 0.1 and 0.524 eV. The occurrence of distinctive dynamical behavior at these two energies is analyzed in some detail. An extensive comparison with previous experimental measurements on the Rydberg H atom with D2 molecules has been carried out at the higher collision energy. In particular, the present theoretical results have been employed to perform simulations of the experimental kinetic energy spectra.

Vibrational excitation through tug-of-war inelastic collisions

Vibrationally inelastic scattering is a fundamental collision process that converts some of the kinetic energy of the colliding partners into vibrational excitation,. The conventional wisdom is that collisions with high impact parameters (where the partners only ‘graze’ each other) are forward scattered and essentially elastic, whereas collisions with low impact parameters transfer a large amount of energy into vibrations and are mainly back scattered. Here we report experimental observations of exactly the opposite behaviour for the simplest and most studied of all neutral–neutral collisions: we find that the inelastic scattering process H + D2(v = 0, j = 0, 2) → H + D2(v′ = 3, j′ = 0, 2, 4, 6, 8) leads dominantly to forward scattering (v and j respectively refer to the vibrational and rotational quantum numbers of the D2 molecule). Quasi-classical trajectory calculations show that the vibrational excitation is caused by extension, not compression, of the D–D bond through interaction with the passing H atom. However, the H–D interaction never becomes strong enough for capture of the H atom before it departs with diminished kinetic energy; that is, the inelastic scattering process is essentially a frustrated reaction in which the collision typically excites the outward-going half of the H–D–D symmetric stretch before the H–D2 complex dissociates. We suggest that this ‘tug of war’ between H and D2 is a new mechanism for vibrational excitation that should play a role in all neutral–neutral collisions where strong attraction can develop between the collision partners.

Experimental and quantum mechanical study of the H+D2 reaction near 0.5 eV: The assessment of the H3 potential energy surfaces

The hydrogen exchange reaction in its H+D2(v=0,j=0)→HD(v′=0,j′)+D isotopic variant has been investigated theoretically and experimentally at the collision energies 0.52 eV, 0.531 eV and 0.54 eV. A detailed comparison of converged quantum mechanical scattering calculations and state-to-state molecular beam experiments has allowed a direct assessment of the quality of the different ab initio potential energy surfaces used in the calculations, and strongly favors the newly refined version of the Boothroyd–Keogh–Martin–Peterson surface. The differences found in the calculations are traced back to slight differences in the topology of the potential energy surfaces.

Dissociation dynamics of acetylene Rydberg states as a function of excited state lifetime

The state selective photodissociation of acetylene, C2H2/C2D2, was studied in the wavelength range 121.2–132.2 nm by high resolution Rydberg atom time-of-flight measurements on the atomic fragment, H/D. In the wavelength region studied members of all four Rydberg series and the highly excited Ẽ valence state were state selectively excited using tunable vacuum-ultraviolet laser radiation. The lifetime of the excited states which were studied varied from 58 fs to more than 2 ps. Formation of the ethynyl radical in its X electronic ground state and its first electronically excited A state is observed with practically no indication of B state fragments. Two decay channels with different dissociation dynamics were also observed. In both channels the observed decay dynamics depended strongly on the excited state of the parent molecule. Further there are major differences between these two dissociation pathways with respect to the measured internal energy and angular distributions. In one channel the dissociat...