Oskar Asvany

H3++H2 isotopic system at low temperatures: Microcanonical model and experimental study

State-to-state thermal rate coefficients for reactions of all H(3)(+) + H(2) isotopic variants are derived and compared to new experimental data. The theoretical data are also sought for astrochemical modeling of cold environments (<50 K). The rates are calculated on the basis of a microcanonical approach using the Langevin model and the conservation laws of mass, energy, angular momentum, and nuclear spin. Full scrambling of all five nuclei during the collision is assumed for the calculations and alternatively partial dynamical restrictions are considered. The ergodic principle of the collision is employed in two limiting cases, neglecting (weak ergodic limit) or accounting for explicit degeneracies of the reaction mechanisms (strong ergodic limit). The resulting sets of rate coefficients are shown to be consistent with the detailed balance and thermodynamical equilibrium constants. Rate coefficients, k(T), for the deuteration chain of H(3)(+) with HD as well as H(2)D(+)/H(3)(+) equilibrium ratios have been measured in a variable temperature 22-pole ion trap. In particular, the D(2)H(+) + HD --> D(3)(+) + H(2) rate coefficient indicates a change in reaction mechanism when going to higher temperatures. The good overall agreement between experiment and theory encourages the use of the theoretical predictions for astrophysical modeling.

Crossed beam reaction of cyano radicals with hydrocarbon molecules. IV. Chemical dynamics of cyanoacetylene (HCCCN; X 1Σ+) formation from reaction of CN(X 2Σ+) with acetylene, C2H2(X 1Σg+)

The chemical reaction dynamics to form cyanoacetylene, HCCCN (X 1Σ+), via the radical–neutral reaction of cyano radicals, CN(X 2Σ+;ν=0), with acetylene, C2H2(X 1Σg+), are unraveled in crossed molecular beam experiments at two collision energies of 21.1 and 27.0 kJ mol−1. Laboratory angular distributions and time-of-flight spectra of the HCCCN product are recorded at m/e=51 and 50. Experiments were supplemented by electronic structure calculations on the doublet C3H2N potential energy surface and RRKM investigations. Forward-convolution fitting of the crossed beam data combined with our theoretical investigations shows that the reaction has no entrance barrier and is initiated by an attack of the CN radical to the π electron density of the acetylene molecule to form a doublet cis/trans HCCHCN collision complex on the 2A′ surface via indirect reactive scattering dynamics. Here 85% of the collision complexes undergo C–H bond rupture through a tight transition state located 22 kJ mol−1 above the cyanoacetylen...

Crossed beam reaction of cyano radicals with hydrocarbon molecules. III. Chemical dynamics of vinylcyanide (C2H3CN;X 1A′) formation from reaction of CN(X 2Σ+) with ethylene, C2H4(X 1Ag)

The neutral–neutral reaction of the cyano radical, CN(X 2Σ+), with ethylene, C2H4(X 1Ag), has been performed in a crossed molecular beams setup at two collision energies of 15.3 and 21.0 kJ mol−1 to investigate the chemical reaction dynamics to form vinylcyanide, C2H3CN(X 1A′) under single collision conditions. Time-of-flight spectra and the laboratory angular distributions of the C3H3N products have been recorded at mass-to-charge ratios 53−50. Forward-convolution fitting of the data combined with ab initio calculations show that the reaction has no entrance barrier, is indirect (complex forming reaction dynamics), and initiated by addition of CN(X 2Σ+) to the π electron density of the olefin to give a long-lived CH2CH2CN intermediate. This collision complex fragments through a tight exit transition state located 16 kJ mol−1 above the products via H atom elimination to vinylcyanide. In a second microchannel, CH2CH2CN undergoes a 1,2 H shift to form a CH3CHCN intermediate prior to a H atom emission via a ...

Crossed beam reaction of cyano radicals with hydrocarbon molecules. I. Chemical dynamics of cyanobenzene (C6H5CN; X 1A1) and perdeutero cyanobenzene (C6D5CN; X 1A1) formation from reaction of CN(X 2Σ+) with benzene C6H6(X 1A1g), and d6-benzene C6D6(X 1A1g)

The chemical reaction dynamics to form cyanobenzene C6H5CN(X 1A1), and perdeutero cyanobenzene C6D5CN(X 1A1) via the neutral–neutral reaction of the cyano radical CN(X 2Σ+), with benzene C6H6(X 1A1g) and perdeutero benzene C6D6(X 1A1g), were investigated in crossed molecular beam experiments at collision energies between 19.5 and 34.4 kJ mol−1. The laboratory angular distributions and time-of-flight spectra of the products were recorded at mass to charge ratios m/e=103–98 and 108–98, respectively. Forward-convolution fitting of our experimental data together with electronic structure calculations (B3LYP/6−311+G**) indicate that the reaction is without entrance barrier and governed by an initial attack of the CN radical on the carbon side to the aromatic π electron density of the benzene molecule to form a Cs symmetric C6H6CN(C6D6CN) complex. At all collision energies, the center-of-mass angular distributions are forward–backward symmetric and peak at π/2. This shape documents that the decomposing intermed...

Laboratory investigation on the formation of unsaturated nitriles in Titan’s atmosphere

Crossed molecular beam experiments of ground state cyano radicals, CN(X 2 S + ), with hydrocarbons acetylene (C2H2), ethylene (C2H4), methylacetylene (CH3CCH), allene (H2CCCH2), dimethylacetylene (CH3CCCH3), and benzene (C6H6,) were performed to investigate the formation of unsaturated nitriles in Titan’s atmosphere. These radical‐neutral reactions have no entrance barrier, depict an exit barrier well below the energy of the reactant molecules, and are all exothermic. The CN radical attacks the p electron density at the olefine, alkyne, and aromatic molecules; the formation of an initial addition complex is a common pathway on the involved potential energy surfaces for all reactions. A subsequent carbon‐hydrogen bond rupture yields the unsaturated nitriles HCCCN, C2H3CN, CH3CCCN, H2CCCH(CN), H2CCCH2CN, and C6H5CN as detected in our experiments. The explicit identification of this CN vs H atom exchange pathway under single collision, makes this reaction-class a compelling candidate to synthesize unsaturated nitriles in Titan’s atmosphere. This versatile concept makes it even possible to predict the formation of nitriles once the corresponding unsaturated hydrocarbons are identified in Titan. Here, the C2H2 as well as cyanoacetylene, HCCCN, have been already identified unambiguously in Titan’s troposphere. Those nitriles as sampled in our crossed beam experiments resemble an ideal challenge to be detected in the framework of the NASA‐ESA Cassini‐Huygens

Experimental ground-state combination differences of CH5+

High-resolution spectroscopy helps to elucidate the highly dynamic structure of protonated methane. [Also see Perspective by Oka] Getting a handle on the CH5+ spectrum Protonated methane, CH5+, fascinates chemists because it seems to break the rules. Theres no obvious place for the fifth hydrogen to bind, and so what happens is that all five hydrogens shuffle about like participants in an endless round of a musical-chairs game. And yet, the molecule has a vibrational spectrum that suggests some semblance of tighter ordering. Asvany et al. have now measured high-resolution vibrational spectra at two low temperatures (10 and 4 Kelvin). Their accompanying analysis makes headway on assigning the peaks and enhancing understanding of the molecules dynamic structure. Science, this issue p. 1346 Protonation of methane (CH4), a rather rigid molecule well described by quantum mechanics, produces CH5+, a prototypical floppy molecule that has eluded definitive spectroscopic description. Experimental measurement of high-resolution spectra of pure CH5+ samples poses a formidable challenge. By applying two types of action spectroscopy predicated on photoinduced reaction with CO2 and photoinhibition of helium cluster growth, we obtained low-temperature, high-resolution spectra of mass-selected CH5+. On the basis of the very high accuracy of the line positions, we determined a spectrum of combination differences. Analysis of this spectrum enabled derivation of equally accurate ground state–level schemes of the corresponding nuclear spin isomers of CH5+, as well as tentative quantum number assignment of this enfant terrible of molecular spectroscopy.

Chemical dynamics of d1-methyldiacetylene (CH3CCCCD; X 1A1) and d1-ethynylallene (H2CCCH(C2D); X 1A′) formation from reaction of C2D(X 2Σ+) with methylacetylene, CH3CCH(X 1A1)

The crossed beam reaction of the d1-ethynyl radical C2D(X 2Σ+), with methylacetylene, CH3CCH(X 1A1), was investigated at an average collision energy of 39.8 kJ mol−1. Our experimental results were combined with electronic structure calculations. The chemical reaction dynamics are indirect, involve three distinct channels, and are initiated via a barrierless addition of C2D to the acetylenic bond through long lived cis and trans CH3CCH(C2D), 1-ethynylpropen-2-yl, intermediates. The reduced cone of acceptance of the carbon atom holding the methyl group favors a carbon–carbon σ bond formation at the carbon atom adjacent to the acetylenic hydrogen atom. A crossed beam experiment of C2D with partially deuterated methylacetylene, CD3CCH, shows explicitly that the reactive intermediates decompose to form both methyldiacetylene, CD3CCCCD (channel 1, 70%–90%), and to a minor amount ethynylallene, D2CCCH(C2D) (channel 2; 10%–30%), isomers through exit transition states located 7–15 kJ mol−1 above the products. The ...

Crossed beam reaction of cyano radicals with hydrocarbon molecules. II. Chemical dynamics of 1-cyano-1-methylallene (CNCH3CCCH2;X 1A′) formation from reaction of CN(X 2Σ+) with dimethylacetylene CH3CCCH3 (X 1A1′)

Marcus ~RRKM! calculations. Forward convolution fitting of the laboratory angular distribution together with the time-of-flight spectra verify that the reaction is indirect and proceeds by addition of the CN radical to the p orbital to form a cis/trans CH3CNCvCCH3 radical intermediate. This decomposes via a rather lose exit transition state located only 6‐7 kJ mol 21 above the products to CNCH3CCCH2 and atomic hydrogen. The best fit of the center-of-mass angular distribution is forward‐backward symmetric and peaks at p/2 documenting that the fragmenting intermediate holds a lifetime longer than its rotational period. Further, the hydrogen atom leaves almost perpendicular to the C5H5N plane resulting in sideways scattering. This finding, together with low frequency bending and wagging modes, strongly support our electronic structure calculations showing a H‐C‐Cangle of about 106.5° in the exit transition state. The experimentally determined reaction exothermicity of 90620 kJ mol 21 is consistent with the theoretical value, 80.4 kJ mol 21 . Unfavorable kinematics prevent us from observing the CN versus CH3 exchange channel, even though our RRKM calculations suggest that this pathway is more important. Since the title reaction is barrierless and exothermic, and the exit transition state is well below the energy of the reactants, this process might be involved in the formation of unsaturated nitriles even in the coldest interstellar environments such as dark, molecular clouds and the saturnian satellite Titan.

Overtone spectroscopy of H2D+ and D2H+ using laser induced reactions.

The method of laser induced reaction is used to obtain high-resolution IR spectra of H2D+ and D2H+ in collision with n-H2 at a nominal temperature of 17 K. For this purpose three cw-laser systems have been coupled to a 22-pole ion trap apparatus, two commercial diode laser systems in the ranges of 6100-6600 cm(-1) and 6760-7300 cm(-1), respectively, and a high-power optical parametric oscillator tunable in the range of 2600-3200 cm(-1). In total, 27 new overtone and combination transitions have been detected for H2D+ and D2H+, as well as a weak line in the nu1 vibrational band of H2D+ (2(20)<--1(01)) at 3164.118 cm(-1). The line positions are compared to high accuracy ab initio calculations, showing small but mode-dependent differences, being largest for three vibrational quanta in the nu2 symmetric bending of H2D+. Within the experimental accuracy, the relative values of the ab initio predicted Einstein B coefficients are confirmed.

A versatile source to produce high-intensity, pulsed supersonic radical beams for crossed-beam experiments: The cyanogen radical CN(X2Σ+) as a case study

In our laboratory a novel and convenient technique has been developed to generate an intense pulsed cyano radical beam to be employed in crossed molecular beam experiments investigating the chemical dynamics of bimolecular reactions. CN radicals in their ground electronic state 2Σ+ are produced in situ via laser ablation of a graphite rod at 266 nm and 30 mJ output power and subsequent reaction of the ablated species with molecular nitrogen, which acts also as a seeding gas. A chopper wheel located after the ablation source and before the collision center selects a 9 μs segment of the beam. By changing the delay time between the pulsed valve and the choppper wheel, we can select a section of the pulsed CN(X2Σ+) beam choosing different velocities in the range of 900–1920 ms−1 with speed ratios from 4 to 8. A high-stability analog oscillator drives the motor of the chopper wheel (deviations less than 100 ppm of the period), and a high-precision reversible motor driver is interfaced to the rotating carbon ro...