Product Internal Energy Research Articles

Dynamics of the HCl + C2H5 Multichannel Reaction on a Full-Dimensional Ab Initio Potential Energy Surface.

We report a full-dimensional ab initio analytical potential energy surface (PES), which accurately describes the HCl + C2H5 multichannel reaction. The new PES is developed by iteratively adding selected configurations along HCl + C2H5 quasi-classical trajectories (QCTs), thereby improving our previous Cl(2P3/2) + C2H6 PES using the Robosurfer program package. QCT simulations for the H'Cl + C2H5 reaction reveal hydrogen-abstraction, chlorine-abstraction, and hydrogen-exchange channels leading to Cl + C2H5H', H' + C2H5Cl, and HCl + C2H4H', respectively. Hydrogen abstraction dominates in the collision energy (Ecoll) range of 1-80 kcal/mol and proceeds with indirect isotropic scattering at low Ecoll and forward-scattered direct stripping at high Ecoll. Chlorine abstraction opens around 40 kcal/mol collision energy and becomes competitive with hydrogen abstraction at Ecoll = 80 kcal/mol. A restricted opening of the cone of acceptance in the Cl-abstraction reaction is found to result in the preference for a backward-scattering direct-rebound mechanism at all energies studied. Initial attack-angle distributions show mainly side-on collision preference of C2H5 for both abstraction reactions, and in the case of the HCl reactant, H/Cl-side preference for the H/Cl abstraction. For hydrogen abstraction, the collision energy transfer into the product translational and internal energy is almost equally significant, whereas in the case of chlorine abstraction, most of the available energy goes into the internal degrees of freedom. Hydrogen exchange is a minor channel with nearly constant reactivity in the Ecoll range of 10-80 kcal/mol.

Imaging the Ion-Molecule Reaction Dynamics of O- + CD4.

While neutral reactions involved in methane oxidation have been intensively studied, much less information is known about the reaction dynamics of the oxygen radical anion with methane. Here, we study the scattering dynamics of this anion-molecule reaction using crossed-beam velocity map imaging with deuterated methane. Differential scattering cross sections for the deuterium abstraction channel have been determined at relative collision energies between 0.2 and 1.5 eV and ab initio calculations of the important stationary points along the reaction pathway have been performed. At lower collision energies, direct backscattering and indirect complex-mediated reaction dynamics are observed, whereas at higher energies, sideways deuterium stripping dominates the reaction. Above 0.7 eV collision energy, a suppressed cross section is observed at low product ion velocities, which is likely caused by the endoergic pathway of combined deuteron/deuterium transfer, forming heavy water. The measured product internal energy is attributed mainly to the low-lying deformation and out-of-plane bending vibrations of the methyl radical product. The results are compared with a previous crossed-beam result for the reaction of oxygen anions with nondeuterated ̧methane and with the related neutral-neutral reactions, showing similar dynamics and qualitative agreement.

Detailed quasiclassical dynamics of the F- + SiH3Cl multi-channel reaction.

We report a detailed quasiclassical trajectory study on the F- + SiH3Cl multi-channel reaction using a full-dimensional ab initio analytical potential energy surface. Reaction probabilities, cross sections, initial attack and scattering angle distributions as well as product relative translational, internal, vibrational, and rotational energy distributions are obtained in the collision energy range of 1-40 kcal mol-1 for the following channels: SiH3F + Cl-, SiH2Cl- + HF, SiH2F- + HCl, SiH2FCl + H-, SiH2 + FHCl-, and SiHFCl- + H2. All the channels are translationally cold indicating indirect mechanisms, except proton transfer (SiH2Cl- + HF), which shows mixed direct-indirect character. The angular distributions vary depending on collision energy and inversion/retention for SiH3F + Cl-. In the case of SiH2Cl- + HF front-side/back-side attack backward-forward/forward scattering preference is found at low/high collision energy. SiH2F- + HCl is formed with isotropic scattering and the preferred angle of attack is similar to the SiH3F + Cl- channel. SiH2FCl + H-/SiH2 + FHCl- favors back-side attack and isotropic/backward scattering, whereas SiHFCl- + H2 does not show significant angular preference.

Details of exit channel dynamics of the ozonolysis of catechol in condensed phase: Product channels and product energy partitioning

Direct dynamics simulations on the ozonolysis reaction of catechol is performed in a vacuum and in an N2 bath to study the various aspects of the exit channel dynamics of the reaction. The simulations were conducted at 20 and 324 kg/m3 densities, with 200 and 293 N2 molecules in the bath, respectively. It is a post-transition state (TS) direct dynamics simulation, where the TS of the catechol+O3 system is taken as the reactant. High combustion temperatures of 800, 1000, and 1500 K are considered for the reactant excitation. In contrast, the bath is taken at 300 K. CO, H2O, CO2, O2, and small carboxylic acid (SCA) are the major channels observed for this reaction. Explicit study of the product channels along with rate constants of all the product channels are obtained. The rate constants are in the order of ns−1. The partitioning of the product's internal energy into its various modes and how the energy transfer occurs in the formation of the products is an exciting aspect of the study. Also reported in this work is the branching ratio of the products and comparison with the experimentally reported data. The energy partitioning study reveals that the dissociation dynamics of the catechol-O3 TS is not statistical. In contrast, the bath dynamics, which correspond to the energy transfer from the TS to the bath, is statistical in nature.

Dynamics of the Cl- + CH3I reaction on a high-level abinitio analytical potential energy surface.

We have developed a full-dimensional analytical abinitio potential energy surface (PES) for the Cl- + CH3I reaction using the Robosurfer program system. The energy points have been computed using a robust composite method defined as CCSD-F12b + BCCD(T) - BCCD with the aug-cc-pVTZ(-PP) basis set and have been fitted by the permutationally invariant polynomial approach. Quasi-classical trajectory simulations on the new PES reveal that two product channels are open in the collision energy (Ecoll) range of 1-80 kcal/mol, i.e., SN2 leading to I- + CH3Cl and iodine abstraction (above ∼45 kcal/mol) resulting in ICl- + CH3. Scattering angle, initial attack angle, product translational energy, and product internal energy distributions show that the SN2 reaction is indirect at low Ecoll and becomes direct-rebound-back-side (CH3-side) attack-type, as Ecoll increases. Iodine abstraction mainly proceeds with direct stripping mechanism with side-on/back-side attack preference. Comparison with crossed-beam experiments and previous direct dynamics simulations shows quantitative or qualitative agreement and also highlights possible theoretical and/or experimental issues motivating further research.

Full-dimensional automated potential energy surface development and dynamics for the OH + C2H6 reaction.

We develop a full-dimensional analytical potential energy surface (PES) for the OH + C2H6 reaction using the Robosurfer program system, which automatically (1) selects geometries from quasi-classical trajectories, (2) performs ab initio computations using a coupled-cluster singles, doubles, and perturbative triples-F12/triple-zeta-quality composite method, (3) fits the energies utilizing the permutationally invariant monomial symmetrization approach, and (4) iteratively improves the PES via steps (1)-(3). Quasi-classical trajectory simulations on the new PES reveal that hydrogen abstraction leading to H2O + C2H5 dominates in the collision energy range of 10-50 kcal/mol. The abstraction cross sections increase and the dominant mechanism shifts from rebound (small impact parameters and backward scattering) to stripping (larger impact parameters and forward scattering) with increasing collision energy as opacity functions and scattering angle distributions indicate. The abstraction reaction clearly favors side-on OH attack over O-side and the least-preferred H-side approach, whereas C2H6 behaves like a spherical object with only slight C-C-perpendicular side-on preference. The collision energy efficiently flows into the relative translation of the products, whereas product internal energy distributions show only little collision energy dependence. H2O/C2H5 vibrational distributions slightly/significantly violate zero-point energy and are nearly independent of collision energy, whereas the rotational distributions clearly blue-shift as the collision energy increases.

Detailed quasiclassical dynamics of the F- + CH3Br reaction on an ab initio analytical potential energy surface.

Dynamics and mechanisms of the F- + CH3Br(v = 0) → Br- + CH3F (SN2 via Walden inversion, front-side attack, and double inversion), F- + inverted-CH3Br (induced inversion), HF + CH2Br- (proton abstraction), and FH⋯Br- + 1CH2 reactions are investigated using a high-level global ab initio potential energy surface, the quasiclassical trajectory method, as well as non-standard configuration- and mode-specific analysis techniques. A vector-projection method is used to identify inversion and retention trajectories; then, a transition-state-attack-angle-based approach unambiguously separates the front-side attack and the double-inversion retention pathways. The Walden-inversion SN2 channel becomes direct rebound dominated with increasing collision energy as indicated by backward scattering, initial back-side attack preference, and the redshifting of product internal energy peaks in accord with CF stretching populations. In the minor retention and induced-inversion pathways, almost the entire available energy transfers into product rotation-vibration, and retention mainly proceeds with indirect, slow double inversion following induced inversion with about 50% probability. Proton abstraction is dominated by direct stripping (evidenced by forward scattering) with CH3-side initial attack preference, providing mainly vibrationally ground state products with significant zero-pointenergy violation.

Final-State-Resolved Dynamics of the H3+ + CO → H2 +HCO+/HOC+ Reaction: A Quasi-Classical Trajectory Study.

The ion-molecule reaction H3+ + CO → H2 + HCO+/HOC+, which initiates the formation of crucial organic molecules, plays a key role in interstellar and circumstellar environments. In this work, the quasi-classical trajectory method is employed to study the reaction dynamics on a recently developed full-dimensional global potential energy surface (PES). The calculated product internal energy distributions and relative internal excited fractions agree reasonably well with the experimental measurements. For the two reaction channels, most of the available energy flows into the vibrational modes of HCO+ or HOC+ at low collision energies, followed by the translational mode and the rotational modes of HCO+ or HOC+. As the collision energy increases, the proportion of the product translational energy increases while the proportion of the product vibrational energy decreases. Furthermore, the CH and CO stretching modes and their combination bands are effectively excited for the product HCO+ while the bending mode is remarkably excited for the product HOC+.

Dynamics of proton transfer from ArH+ to CO

The reaction of ArH+ with CO is a fast proton transfer reaction that can form two different isomers, HCO+ and HOC+. It has been investigated in a crossed beam experiment and with direct dynamics simulations at collision energies ranging from 0.4 to 2.4 eV. Images of the differential cross sections reveal dominant forward scattering, which is evidence for direct dynamics. The measured product internal energies are primarily determined by the reaction enthalpy and only at large scattering angles depend noticeably on the collision energy. The computational results agree well with the measured internal energy and scattering angle distributions and with the previously measured total rate constant. The direct reaction dynamics with dominant forward scattering are well reproduced by the almost step like opacity functions. The HCO+/HOC+ branching is found to be close to 2:1 in the simulations at 0.83 eV and 2.37 eV collision energy. A mode-specific vibrational analysis provides further insight into the isomer specific distribution of the product internal excitation.

Mode-Specific Quasiclassical Dynamics of the F- + CH3I SN2 and Proton-Transfer Reactions.

Mode-specific quasiclassical trajectory computations are performed for the F- + CH3I( v k = 0, 1) SN2 and proton-transfer reactions at nine different collision energies in the range of 1.0-35.3 kcal/mol using a full-dimensional high-level ab initio analytical potential energy surface with ground-state and excited CI stretching ( v3), CH3 rocking ( v6), CH3 umbrella ( v2), CH3 deformation ( v5), CH symmetric stretching ( v1), and CH asymmetric stretching ( v4) initial vibrational modes. Millions of trajectories provide statistically definitive mode-specific cross sections, opacity functions, scattering angle distributions, and product internal energy distributions. The excitation functions reveal slight vibrational SN2 inversion inhibition/enhancement at low/high collision energies ( Ecoll), whereas large decaying-with- Ecoll vibrational enhancement effects for the SN2 retention (double inversion) and proton-transfer channels. The most efficient vibrational enhancement is found by exciting the CI stretching (high Ecoll) for SN2 inversion and the CH stretching modes (low Ecoll) for double inversion and proton transfer. Mode-specific effects do not show up in the scattering angle distributions and do blue-shift the hot/cold SN2/proton-transfer product internal energies.

Temperature dependence of the photodissociation of CO2 from high vibrational levels: 205-230 nm imaging studies of CO(X1Σ+) and O(3P, 1D) products.

The 205-230 nm photodissociation of vibrationally excited CO2 at temperatures up to 1800 K was studied using Resonance Enhanced Multiphoton Ionization (REMPI) and time-sliced Velocity Map Imaging (VMI). CO2 molecules seeded in He were heated in an SiC tube attached to a pulsed valve and supersonically expanded to create a molecular beam of rotationally cooled but vibrationally hot CO2. Photodissociation was observed from vibrationally excited CO2 with internal energies up to about 20 000 cm-1, and CO(X1Σ+), O(3P), and O(1D) products were detected by REMPI. The large enhancement in the absorption cross section with increasing CO2 vibrational excitation made this investigation feasible. The internal energies of heated CO2 molecules that absorbed 230 nm radiation were estimated from the kinetic energy release (KER) distributions of CO(X1Σ+) products in v″ = 0. At 230 nm, CO2 needs to have at least 4000 cm-1 of rovibrational energy to absorb the UV radiation and produce CO(X1Σ+) + O(3P). CO2 internal energies in excess of 16 000 cm-1 were confirmed by observing O(1D) products. It is likely that initial absorption from levels with high bending excitation accesses both the A1B2 and B1A2 states, explaining the nearly isotropic angular distributions of the products. CO(X1Σ+) product internal energies were estimated from REMPI spectroscopy, and the KER distributions of the CO(X1Σ+), O(3P), and O(1D) products were obtained by VMI. The CO product internal energy distributions change with increasing CO2 temperature, suggesting that more than one dynamical pathway is involved when the internal energy of CO2 (and the corresponding available energy) increases. The KER distributions of O(1D) and O(3P) show broad internal energy distributions in the CO(X1Σ+) cofragment, extending up to the maximum allowed by energy but peaking at low KER values. Although not all the observations can be explained at this time, with the aid of available theoretical studies of CO2 VUV photodissociation and O + CO recombination, it is proposed that following UV absorption, the two lowest lying triplet states, a3B2 and b3A2, and the ground electronic state are involved in the dynamical pathways that lead to product formation.

Quasiclassical dynamics for the H + HS abstraction and exchange reactions on the 3A″ and the 3A′ states

A detailed quasiclassical trajectory study of the H + HS reaction yielding an exchange (H + HS) and an abstraction (H2 + S) channel has been performed by employing the new triplet (3)A" and (3)A' surfaces developed by our group. The cross sections for both channels are presented and found to be in good agreement with previous quantum wave packet results. The thermal rate coefficients for abstraction channel at the temperature between 200 and 1000 K have been evaluated by averaging over a Boltzmann distribution of rotational states and compared with the available experimental values. It is found that the thermal rate coefficients exhibit a conventional Arrhenius-type dependence on temperature, which agrees well with the experimental data. Average fractions, vibration and rotation distributions of the products H2 and HS at different collision energies have been also fully investigated. Furthermore, influence of the collision energy on the total and product-state-resolved differential cross sections (DCSs) for both channels are calculated and discussed. Some observations on the mechanism of the title reaction have been made; in particular it was discovered that reactive collisions along the collinear pathway cause the H2 product to scatter backward, while the reactive collisions with large impact parameters b, which are favored deviating from the minimum energy path, produced mainly forward scattering. For the exchange channel, the discrepancies in the DCS are also distinguished through an analysis of individual trajectories and found a double microscopic mechanism, migration or non-migration. The state-to-state DCSs provide a global perspective of the reaction mechanisms and their contribution to the final product internal energy states. The theoretical findings are discussed and compared with a kinematic constraint model.

Classical dynamics of state-resolved hyperthermal O(3P) + H2O(1A1) collisions

Classical dynamics calculations are performed for O((3)P) + H2O((1)A1) collisions from 2 to 10 km s(-1) (4.1-101.3 kcal mol(-1)), focusing on product internal energies. Several methods are used to produce ro-vibrationally state-resolved product cross sections and to enforce zero-point maintenance from analysis of the classical trajectories. Two potential energy surfaces are used: (1) a recently developed set of global reactive surfaces for the three lowest triplet states which model OH formation, H elimination to make H + OOH, O-atom exchange, and collisional excitation and (2) a non-reactive surface used in past classical and quantum collision studies. Comparisons to these previous studies suggest that for H2O vibrational excitation, classical dynamics which include gaussian binning procedures and/or selected zero-point maintenance algorithms can produce results which approximate quantum scattering cross sections fairly well. Without these procedures, the classical cross sections can be many orders of magnitude greater than the quantum cross sections for exciting the bending vibration of H2O, especially near threshold. The classical cross section over-estimate is due to energy borrowing from stretching modes which dip below zero-point values. For results on the reactive surfaces, the present calculations show that at higher velocities there is an unusually large amount of product internal excitation. For OOH, where 40% of available collision energy goes into internal motion, the excited product vibrational and rotational energy distributions are relatively flat and values of the OOH rotational angular momentum exceed J = 100. Other product channel distributions show an exponential fall-off with energy consistent with an energy gap law. The present detailed distributions and cross sections can serve as a guide for future hyperthermal measurements of this system.

Indirect Dynamics in a Highly Exoergic Substitution Reaction

The highly exoergic nucleophilic substitution reaction F(-) + CH3I shows reaction dynamics strikingly different from that of substitution reactions of larger halogen anions. Over a wide range of collision energies, a large fraction of indirect scattering via a long-lived hydrogen-bonded complex is found both in crossed-beam imaging experiments and in direct chemical dynamics simulations. Our measured differential scattering cross sections show large-angle scattering and low product velocities for all collision energies, resulting from efficient transfer of the collision energy to internal energy of the CH3F reaction product. Both findings are in strong contrast to the previously studied substitution reaction of Cl(-) + CH3I [Science 2008, 319, 183-186] at all but the lowest collision energies, a discrepancy that was not captured in a subsequent study at only a low collision energy [J. Phys. Chem. Lett. 2010, 1, 2747-2752]. Our direct chemical dynamics simulations at the DFT/B97-1 level of theory show that the reaction is dominated by three atomic-level mechanisms, an indirect reaction proceeding via an F(-)-HCH2I hydrogen-bonded complex, a direct rebound, and a direct stripping reaction. The indirect mechanism is found to contribute about one-half of the overall substitution reaction rate at both low and high collision energies. This large fraction of indirect scattering at high collision energy is particularly surprising, because the barrier for the F(-)-HCH2I complex to form products is only 0.10 eV. Overall, experiment and simulation agree very favorably in both the scattering angle and the product internal energy distributions.

Collision Dynamics of O(3P) + DMMP Using a Specific Reaction Parameters Potential Form

Starting from previous benchmark CBS-QB3 electronic structure calculations (Conforti, P. F.; Braunstein, M.; Dodd, J. A. J. Phys. Chem. A 2009, 113, 13752), we develop two global potential energy surfaces for O((3)P) + DMMP collisions, using the specific reaction parameters approach. Each surface is simultaneously fit along the three major reaction pathways: hydrogen abstraction, hydrogen elimination, and methyl elimination. We then use these surfaces in classical dynamics simulations and compute reactive cross sections from 4 to 10 km s(-1) collision velocity. We examine the energy disposal and angular distributions of the reactive and nonreactive products. We find that for reactive collisions, an unusually large amount of the initial collision energy is transformed into internal energy. We analyze the nonreactive and reactive product internal energy distributions, many of which fit Boltzmann temperatures up to ~2000 K.

Communication: New insight into the barrier governing CO2 formation from OH + CO

Despite its relative simplicity, the role of tunneling in the reaction OH + CO → H + CO(2) has eluded the quantitative predictive powers of theoretical reaction dynamics. In this study a one-dimensional effective barrier to the formation of H + CO(2) from the HOCO intermediate is directly extracted from dissociative photodetachment experiments on HOCO and DOCO. Comparison of this barrier to a computed minimum-energy barrier shows that tunneling deviates significantly from the calculated minimum-energy pathway, predicting product internal energy distributions that match those found in the experiment and tunneling lifetimes short enough to contribute significantly to the overall reaction. This barrier can be of direct use in kinetic and statistical models and aid in the further refinement of the potential energy surface and reaction dynamics calculations for this system.

Photodissociation dynamics of acetylene via the C̃ Π1u electronic state

Photodissociation of acetylene has been studied using the H-atom Rydberg tagging time-of-flight technique at two excitation wavelengths (148.35 and 151.82 nm) in the vacuum ultraviolet region. Product translational energy distributions have been obtained from the H-atom time-of-flight spectra. Experimental results indicate that the C(2)H product is mainly populated in the A state. Clear trans-bend nu(2) and C-C stretch nu(3) vibrational progressions of the C(2)H(A) product in the product internal energy distribution were observed. The anisotropy parameter obtained from experiment is clearly translational energy dependent for both photolysis wavelengths. The anisotropy parameters at the two photolysis wavelengths were also found to be significantly different from each other, suggesting different dissociation dynamics for the two photolysis wavelengths.

Three Reaction Pathways in the H + HCO → H2 + CO Reaction

We report quasiclassical trajectory calculations of the H + HCO --> H(2) + CO reaction using a recent global potential energy surface. Three microscopic pathways are identified for this reaction. One is a direct abstraction, and the others both proceed via initial formation of a long-lived complex in the H(2)CO well followed by reaction (a) over the molecular saddle point transition state or (b) via a roaming pathway previously identified for the unimolecular photodissociation reaction [Townsend et al., Science 2004, 306, 1158]. Cross sections and product internal energy distributions for each pathway are calculated for five initial collision energies.

Direct ab initio molecular dynamics study of F atom reaction with methane

The dynamics of the F + CH4 → HF + CH3 and F + CD4 → DF + CD3 reactions have been investigated using classical trajectory calculations at the MP2/cc-pvdz level of theory. The trajectories were calculated directly from electronic structure computations, and a Hessian based method with updating was used to integrate the trajectories. Using this method, product rovibrational populations and internal energy distributions were obtained for the F + CH4 and F + CD4 reactions. The theoretical results were compared with the available experimental data and previous calculations results. The state distributions of the reaction F + CH4 in these calculations are in reasonable agreement with the experimental results, which indicates that the experimental behavior of the reaction could be well reproduced by the direct classical trajectory calculations at MP2/cc-pvdz level. As such, the product rovibrational populations and internal energy distributions for the reaction F + CD4 were predicted. The same degree of agreement between theory and experiment as the F + CH4 reaction is expected.

Solid Propellant Burning Rate From Strand Burner Pressure Measurement

AbstractStrand burner pressure–time data are analyzed to determine if the propellant burning rate can be extracted. This approach is based on strand burner pressure–time history that is related to the temperature change due to exothermic reaction heating of chamber gases and gas addition to the chamber by propellant combustion products. In support of this method, chemical equilibrium calculations were made to project product composition, internal energy, and other needed properties. A mathematical model was formulated and solved numerically and the calculated burning rates were compared with the experimental wire‐break time results provided simultaneously and with the propellant manufacturer's results, when available. The comparisons reveal that the approach has merit and that more accurate pressure determination coupled with additional thermochemical information and strand burner gas temperature measurements has the potential to make this approach a viable technique and one that can be applied in conjunction with other burning rate measurements. The proposed method is similar to a well‐developed technique which is commonly applied to ballistic powders but with adjustments for the differences in geometry, pressure, and time of event.