Quantum and classical studies of the O(3P) + H2(v = 0-3,j = 0) --> OH + H reaction using benchmark potential surfaces

We present results of time-dependent quantum mechanics (TDQM) and quasiclassical trajectory (QCT) studies of the excitation function for O(3P) + H2(v = 0-3,j = 0) --> OH + H from threshold to 30 kcal/mol collision energy using benchmark potential energy surfaces [Rogers et al., J. Phys. Chem. A 104, 2308 (2000)]. For H2(v = 0) there is excellent agreement between quantum and classical results. The TDQM results show that the reactive threshold drops from 10 kcal/mol for v = 0 to 6 for v = 1, 5 for v = 2 and 4 for v = 3, suggesting a much slower increase in rate constant with vibrational excitation above v = 1 than below. For H2(v > 0), the classical results are larger than the quantum results by a factor approximately 2 near threshold, but the agreement monotonically improves until they are within approximately 10% near 30 kcal/mol collision energy. We believe these differences arise from stronger vibrational adiabaticity in the quantum dynamics, an effect examined before for this system at lower energies. We have also computed QCT OH(v',j') state-resolved cross sections and angular distributions. The QCT state-resolved OH(v') cross sections peak at the same vibrational quantum number as the H2 reagent. The OH rotational distributions are also quite hot and tend to cluster around high rotational quantum numbers. However, the dynamics seem to dictate a cutoff in the energy going into OH rotation indicating an angular momentum constraint. The state-resolved OH distributions were fit to probability functions based on conventional information theory extended to include an energy gap law for product vibrations.     

Comparison of experimental time-of-flight spectra of the HF products from the F+H2 reaction with exact quantum mechanical calculations

High resolution HF product time-of-flight spectra measured for the reactive scattering of F atoms from n-H2(p-H2) molecules at collision energies between 69 and 81 meV are compared with exact coupled-channel quantum mechanical calculations based on the Stark-Werner ab initio ground state potential energy surface. Excellent agreement between the experimental and computed rotational distributions is found for the HF product vibrational states v'=1 and v'=2. For the v'=3 vibrational state the agreement, however, is less satisfactory, especially for the reaction with p-H2. The results for v'=1 and v'=2 confirm that the reaction dynamics for these product states is accurately described by the ground electronic state 1 (2)A' potential energy surface. The deviations for HF(v'=3, j' > or =2) are attributed to an enhancement of the reaction resulting from the 25% fraction of excited ((2)P(12)) fluorine atoms in the reactant beam.     

Product spin-orbit state resolved dynamics of the H+H2O and H+D2O abstraction reactions

The product state-resolved dynamics of the reactions H+H(2)O/D(2)O-->OH/OD((2)Pi(Omega);v',N',f )+H(2)/HD have been explored at center-of-mass collision energies around 1.2, 1.4, and 2.5 eV. The experiments employ pulsed laser photolysis coupled with polarized Doppler-resolved laser induced fluorescence detection of the OH/OD radical products. The populations in the OH spin-orbit states at a collision energy of 1.2 eV have been determined for the H+H(2)O reaction, and for low rotational levels they are shown to deviate from the statistical limit. For the H+D(2)O reaction at the highest collision energy studied the OD((2)Pi(3/2),v'=0,N'=1,A') angular distributions show scattering over a wide range of angles with a preference towards the forward direction. The kinetic energy release distributions obtained at 2.5 eV also indicate that the HD coproducts are born with significantly more internal excitation than at 1.4 eV. The OD((2)Pi(3/2),v'=0,N'=1,A') angular and kinetic energy release distributions are almost identical to those of their spin-orbit excited OD((2)Pi(1/2),v'=0,N'=1,A') counterpart. The data are compared with previous experimental measurements at similar collision energies, and with the results of previously published quasiclassical trajectory and quantum mechanical calculations employing the most recently developed potential energy surface. Product OH/OD spin-orbit effects in the reaction are discussed with reference to simple models.     

State-to-state reaction probabilities for the H+O2(v,j)-->O+OH(v',j') reaction on three potential energy surfaces

We report state-to-state and total reaction probabilities for J=0 and total reaction probabilities for J=2 and 4 for the title reaction, both for ground-state and initially rovibrationally excited reactants. The results for three different potential energy surfaces are compared and contrasted. The potential energy surfaces employed are the DMBE IV surface by Pastrana et al. [J. Phys. Chem. 94, 8073 (1990)], the surface by Troe and Ushakov (TU) [J. Chem. Phys. 115, 3621 (2001)], and the new XXZLG ab initio surface by Xu et al. [J. Chem. Phys. 122, 244305 (2005)]. Our results show that the total reaction probabilities from both the TU and XXZLG surfaces are much smaller in magnitude for collision energies above 1.2 eV compared to the DMBE IV surface. The three surfaces also show different behavior with regards to the effect of initial state excitation. The reactivity is increased on the XXZLG and the TU surfaces and decreased on the DMBE IV surface. Vibrational and rotational product state distributions for the XXZLG and the DMBE IV surface show different behaviors for both types of distributions. Our results show that for energies above 1.25 eV the dynamics on the DMBE IV surface are not statistical. However, there is also evidence that the dynamics on the XXZLG surface are not purely statistical for energies above the onset of the first excited product vibrational state v'=1. The magnitude of the total reaction probability is decreased for J>0 for the DMBE IV and the XXZLG surfaces for ground-state reactants. However, for initially rovibrationally excited reactants, the total reaction probability does not decrease as expected for both surfaces. As a result the total cross section averaged over all Boltzmann accessible rotational states may well be larger than the cross section reported in the literature for j=1.     

Unravelling the reactivity of antisymmetric stretch-excited CH4 with Cl by-product pair-correlation measurements

The vibrational branching ratio [CH(3)(v=0) + HCl(v'=1)]/[CH(3)(v=0) + HCl(v'=0)] of two correlated product pairs from the title reaction shows a dramatic E(c)-dependence, in sharp contrast to the previously observed behavior in Cl + CHD(3)(v(1)=1), while the vibrational enhancement factors in reactivity of the two reactions are remarkably similar.     

Quasi-classical trajectory study of the role of vibrational and translational energy in the Cl(2P) + NH3 reaction

A detailed state-to-state dynamics study was performed to analyze the effects of vibrational excitation and translational energy on the dynamics of the Cl((2)P) + NH(3)(v) gas-phase reaction, effects which are connected to such issues as mode selectivity and Polanyi's rules. This reaction evolves along two deep wells in the entry and exit channels. At low and high collision energies quasi-classical trajectory calculations were performed on an analytical potential energy surface previously developed by our group, together with a simplified model surface in which the reactant well is removed to analyze the influence of this well. While at high energy the independent vibrational excitation of all NH(3)(v) modes increases the reactivity by a factor ≈1.1-2.9 with respect to the vibrational ground-state, at low energy the opposite behaviour is found (factor ≈ 0.4-0.9). However, when the simplified model surface is used at low energy the independent vibrational excitation of all NH(3)(v) modes increases the reactivity, showing that the behaviour at low energies is a direct consequence of the existence of the reactant well. Moreover, we find that this reaction exhibits negligible mode selectivity, first because the independent excitation of the N-H symmetric and asymmetric stretch modes, which lie within 200 cm(-1) of each other, leads to reactions with similar reaction probabilities, and second because the vibrational excitation of the reactive N-H stretch mode is only partially retained in the products. For this "late transition-state" reaction, we also find that vibrational energy is more effective in driving the reaction than an equivalent amount of energy in translation, consistent with an extension of Polanyi's rules. Finally, we find that the non-reactive events, Cl((2)P)+NH(3)(v) → Cl((2)P) + NH(3)(v'), lead to a great number of populated vibrational states in the NH(3)(v') product, even starting from the NH(3)(v = 0) vibrational ground state at low energies, which is unphysical in a quantum world. This result is interpreted on the basis of non-conservation of the ZPE per mode.     

Potential energy surface, kinetics, and dynamics study of the Cl+CH4-->HCl+CH3 reaction

A modified and recalibrated potential energy surface for the gas-phase Cl+CH4-->HCl+CH3 reaction is reported and tested. It is completely symmetric with respect to the permutation of the four methane hydrogen atoms and is calibrated with respect to updated experimental and theoretical stationary point properties and experimental forward thermal rate constants. From the kinetics point of view, the forward and reverse thermal rate constants and the activation energies were calculated using the variational transition-state theory with semiclassical transmission coefficients over a wide temperature range of 150-2500 K. The theoretical results reproduce the available experimental data, with a small curvature of the Arrhenius plot which indicates the role of tunneling in this hydrogen abstraction reaction. A dynamics study was also performed on this PES using quasiclassical trajectory (QCT) calculations, including corrections to avoid zero-point energy leakage along the trajectories. First, we found a noticeable internal energy in the coproduct methyl radical, both in the ground-state [CH4 (v=0)] and vibrationally excited [CH4 (v=1)] reactions. This CH3 internal energy was directly precluded in some experiments or oversimplified in previous theoretical studies using pseudotriatomic models. Second, our QCT calculations give HCl rotational distributions slightly hotter than those in experiment, but correctly describing the experimental trend of decreasing the HCl product rotation excitation in going from HCl (v'=0) to HCl (v'=1) for the CH4 (v=1) reaction. Third, the state specific scattering distributions present a reasonable agreement with experiment, although they tend to make the reaction more forward and backward scattered than found experimentally probably because of the hotter rotational distribution and the deficiencies of the QCT methods.     

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.     

Quasi-classical trajectory study of the F + CD4 reaction dynamics

To analyze the F + CD4 gas-phase abstraction reaction, an exhaustive state-to-state dynamics study was performed. Quasi-classical trajectory (QCT) calculations, including corrections to avoid zero-point energy leakage along the trajectories, were used on an analytical potential energy surface (PES-2006) recently developed by our group for collision energies in the range 0.3-6.0 kcal mol-1. While the CD3 coproduct appears vibrationally and rotationally cold, in agreement with experiment, most of the available energy appears as FD(nu') product vibrational energy, peaking at nu' = 3, one unit colder than experiment. The excitation function reproduces experiment, with the maximum contribution from the most populated FD(nu' = 3) level. The state-specific scattering distributions at different collision energies also reproduce the experimental behavior, with a clear propensity toward forward scattering, this tendency increasing with the energy. These dynamics results show the capacity of the PES-2006 surface to correctly describe the title reaction.     

Photodissociation dynamics of the reaction H2CO-->H+HCO via the singlet (S0) and triplet (T1) surfaces

We have explored the photodissociation dynamics of the reaction H(2)CO+hnu-->H+HCO in the range of 810-2600 cm(-1) above the reaction threshold. Supersonically cooled formaldehyde was excited into selected J(Ka,Kc) rotational states of six vibrational levels (1(1)4(1), 5(1), 2(2)6(1), 2(2)4(3), 2(3)4(1), and 2(4)4(1)) in the A((1)A2) state. The laser induced fluorescence spectra of the nascent HCO fragment provided detailed product state distributions. When formaldehyde was excited into the low-lying levels 1(1)4(1), 5(1), and 2(2)6(1), at E(avail)<1120 cm(-1), the product state distribution can be modeled qualitatively by phase space theory. These dynamics are interpreted as arising from a reaction path on the barrierless S0 surface. When the initial states 2(2)4(3) and 2(3)4(1) were excited (E(avail)=1120-1500 cm(-1)), a second type of product state distribution appeared. This second distribution peaked sharply at low N, Ka and was severely truncated in comparison with those obtained from the lower lying states. At the even higher energy of 2(4)4(1) (E(avail) approximately 2600 cm(-1)) the sharply peaked distribution appears to be dominant. We attribute this change in dynamics to the opening up of the triplet channel to produce HCO. The theoretical height of the barrier on the T1 surface lies between 1700 and 2100 cm(-1) and so we consider the triplet reaction to proceed via tunneling at the intermediate energies and proceed over the barrier at the higher energies. Considerable population was observed in the excited (0,0,1) state for all initial H(2)CO states that lie above the appearance energy. Rotational populations in the (0,0,1) state dropped more rapidly with (N,Ka) than did the equivalent populations in (0,0,0). This indicates that, although individual rotational states are highly populated in (0,0,1), the total v3=1 population might not be so large. Specific population was also measured in the almost isoenergetic Kc and J states. No consistent population preference was found for either asymmetry or spin-rotation component.     

Evidence for excited spin-orbit state reaction dynamics in F+H2: theory and experiment

We describe fully quantum, time-independent scattering calculations of the F+H2-->HF+H reaction, concentrating on the HF product rotational distributions in v'=3. The calculations involved two new sets of ab initio potential energy surfaces, based on large basis set, multireference configuration-interaction calculations, which are further scaled to reproduce the experimental exoergicity of the reaction. In addition, the spin-orbit, Coriolis, and electrostatic couplings between the three quasidiabatic F+H2 electronic states are included. The calculated integral cross sections are compared with the results of molecular beam experiments. At low collision energies, a significant fraction of the reaction is due to Born-Oppenheimer forbidden, but energetically allowed reaction of F in its excited (2P 1/2) spin-orbit state. As the collision energy increases, the Born-Oppenheimer allowed reaction of F in its ground (2P 3/2) spin-orbit state rapidly dominates. Overall, the calculations agree reasonably well with the experiment, although there remains some disagreement with respect to the degree of rotational excitation of the HF(v'=3) products as well as with the energy dependence of the reactive cross sections at the lowest collision energies.     

Exact state-to-state quantum dynamics of the F + HD --> HF(v' = 2) + D reaction on model potential energy surfaces

In this paper, we present the results of a theoretical investigation on the dynamics of the title reaction at collision energies below 1.2 kcal/mol using rigorous quantum reactive scattering calculations. Vibrationally resolved integral and differential cross sections, as well as product rotational distributions, have been calculated using two electronically adiabatic potential energy surfaces, developed by us on the basis of semiempirical modifications of the entrance channel. In particular, we focus our attention on the role of the exothermicity and of the exit channel region of the interaction on the experimental observables. From the comparison between the theoretical results, insight about the main mechanisms governing the reaction is extracted, especially regarding the bimodal structure of the HF(v = 2) nascent rotational state distributions. A good overall agreement with molecular beam scattering experiments has been obtained.     

Al(2Pu)+H2(X1Σ+g)的分子反应动力学

基于多体展式方法所导出的ＡｌＨ２（Ｘ＾２Ａ１）分析势能函数,用准经典的Ｍｏｎｔｅ－Ｃａｒｌｏ轨迹法对Ａｌ（＾２Ｐｕ）＋Ｈ２（Ｘ＾１∑＾＋ｇ,ｕ＝ｊ＝０）的分子反应动力学过程进行了计算。结果表明,此反应的主产物为交换反应Ａｌ（＾２Ｐｕ）＋Ｈ２（Ｘ＾１∑＾＋ｇ,ｖ＝ｊ＝０）→ＡｌＨ（Ｘ＾１∑＾＋,Ｖ’,ｊ’）＋Ｈ（＾２Ｓｇ）的ＡｌＨ（Ｘ＾１∑＾＋,ｖ’,ｊ’）没有发现ＡｌＨ２（Ｘ＾２Ａ１）的络合物。而     

Quantum calculations of the O(3P)+H2-->OH+H reaction

Quantum scattering calculations are reported for the O(3P)+H2(v=0,1) reaction using chemically accurate potential energy surfaces of 3A' and 3A" symmetry. We present state-to-state reaction cross sections and rate coefficients as well as thermal rate coefficients for the title reaction using accurate quantum calculations. Our calculations yield reaction cross sections that are in quantitative accord with results of recent crossed molecular beam experiments. Comparisons with results obtained using the J-shifting calculations show that the J-shifting approximation is quite reliable for this system. Thermal rate coefficients from the exact calculations and the J-shifting approximation agree remarkably well with experimental results. Our calculations also reproduce the markedly different OH(v'=0)/OH(v'=1) branching in O(3P)+H2(v=1) reaction, observed in experiments that use different O(3P) atom sources. In particular, we show that the branching ratio is a strong function of the kinetic energy of the O(3P) atom.     

Quantum and quasiclassical studies of the O(3P)+HCl-->OH+Cl(2P) reaction using benchmark potential surfaces

We have performed quantum mechanical (QM) dynamics calculations within the independent-state approximation with new benchmark triplet A" and A' surfaces [B. Ramachandran et al., J. Chem. Phys. 119, 9590 (2003)] for the rovibronic state-to-state measurements of the reaction O(3P)+HCl(v=2,j=1,6,9)-->OH(v'j')+Cl(2P) [Zhang et al., J. Chem. Phys. 94, 2704 (1991)]. The QM and experimental rotational distributions peak at similar OH(j') levels, but the QM distributions are significantly narrower than the measurements and previous quasiclassical dynamics studies. The OH(low j) populations observed in the measurements are nearly absent in the QM results. We have also performed quasiclassical trajectory with histogram binning (QCT-HB) calculations on these same benchmark surfaces. The QCT-HB rotational distributions, which are qualitatively consistent with measurements and classical dynamics studies using other surfaces, are much broader than the QM results. Application of a Gaussian binning correction (QCT-GB) dramatically narrows and shifts the QCT-HB rotational distributions to be in very good agreement with the QM results. The large QCT-GB correction stems from the special shape of the joint distribution of the classical rotational/vibrational action of OH products. We have also performed QM and QCT calculations for the transition, O+HCl(v=0,T=300 K)-->OH(v'j')+Cl from threshold to approximately 130 kcal mol(-1) collision energy as a guide for possible future hyperthermal O-atom measurements. We find in general a mixed energy release into translation and rotation consistent with a late barrier to reaction. Angular distributions at high collision energy are forward peaked, consistent with a stripping mechanism. Direct collisional excitation channel cross sections, O+HCl(v=0,T=300 K)-->O+HCl(v'=1), in the same energy range are large, comparable in magnitude to the reactive channel cross sections. Although the (3)A" state dominates most collision processes, above approximately 48 kcal mol(-1), the (3)A' state plays the major role in collisional excitation.     

Vibrational and rotational distributions of the CH(A2Delta) product of the C(2)H + O(3P) reaction studied by fourier transform visible (FTVIS) emission spectroscopy

The C(2)H + O((3)P) --> CH(A) + CO reaction is investigated using Fourier transform visible emission spectroscopy. The O((3)P) and C(2)H radicals are produced by simultaneous 193 nm photolysis of SO(2) and C(2)H(2) precursors, respectively. The nascent vibrational and rotational distributions of the CH(A) product are obtained under time-resolved, but quasi-steady-state, conditions facilitated by the short lifetime of the CH(A) emission. The vibrational temperature of the CH(A) product is found to be appreciably hotter (2800 +/- 100 K) than the rotational distributions in the v' = 0 (1400 +/- 100 K) and v' = 1 (1250 +/- 250 K) levels. The results suggest that the reaction may proceed through an electronically excited HCCO() intermediate; moreover, the vibrational excitation compared to rotational excitation is higher than expected based on a statistical distribution of energy and may be the result of geometrical changes in the transition state. The CH(A) emission is also observed in a C(2)H(2)/O/H reaction mixture using a microwave discharge apparatus to form O atoms, with subsequent H atom production. The nascent rotational and vibrational distributions of the CH(A) determined by the microwave discharge apparatus are very similar to the CH(A) distributions obtained in the photodissociation experiment. The results support the idea that the C(2)H + O((3)P) reaction may play a role in low-pressure C(2)H(2)/O/H flames, as previously concluded.     

The dynamics of the Cl+n-C4H10-->HCl (v',j') + C4H9 reaction at 0.32 eV

Rotational state resolved center-of-mass angular scattering and kinetic energy release distributions have been determined for the HCl (v' = 0, j' = 0-6) products of the reaction of chlorine with n-butane using the photon-initiated reaction technique, coupled with velocity-map ion imaging. The angular and kinetic energy release distributions derived from the ion images are very similar to those obtained previously for the Cl plus ethane reaction. The angular distributions are found to shift from forward scattering to more isotropic scattering with increasing HCl rotational excitation. The kinetic energy release distributions indicate that around 30% of the available energy is channeled into internal excitation of the butyl radical products. The data analysis also suggests that H-atom abstraction takes place from both primary and secondary carbon atom sites, with the primary site producing rotationally cold, forward scattered HCl (v' = 0) products, and the secondary site yielding more isotropically scattered HCl (v' = 0) possessing higher rotational excitation. The mechanisms leading to these two product channels are discussed in the light of the present findings, and in comparison with studies of other Cl plus alkane reactions.     

The dissociation dynamics of He...I 35Cl(B,v'=2,3) complexes with varying amounts of internal energy

The He...I (35)Cl intermolecular vibrational levels with n'=0-6 that are bound within the He+ICl(B,v'=3) potential [A. B. McCoy, J. P. Darr, D. S. Boucher, P. R. Winter, M. D. Bradke, and R. A. Loomis, J. Chem. Phys. 120, 2677 (2004)] are identified in laser-induced fluorescence experiments performed at very low temperatures within a supersonic expansion. Comparisons of the positions and intensities of these lines with the excitation spectra, calculated using potential surfaces to describe the interactions between the helium atom and ICl in its ground and excited state, assist in the assignments. Based on these comparisons the excited state potential was rescaled so that the experimental and calculated J'=0 energies agree to within the experimental uncertainties for all but the lowest, n'=0, intermolecular level. Two-laser, action, and pump-probe spectroscopy experiments indicate that the bound He...I (35)Cl(B,v'=3) intermolecular vibrational levels undergo vibrational predissociation forming rotationally excited I (35)Cl(B,v'=2,j') products with distributions that depend upon the initial intermolecular vibrational level excited. Action spectra recorded in the ICl B-X, 2-0 region while monitoring the Deltav=0, I (35)Cl(B,v'=2) channel reveal two additional dissociation mechanisms for the He...I (35)Cl(B,v') excited state complexes: rotational predissociation of discrete metastable states lying slightly above the He+I (35)Cl(B,v'=2) asymptote and direct dissociation that occurs when the linear conformer is excited to the continuum of states above the same asymptote. The rotational predissociation pathway forms I (35)Cl(B,v'=2,j') products in all of the rotational states energetically accessible. The direct dissociation mechanism yields very cold rotational product state distributions; for instance, the average rotational energy in the product state distribution measured when the linear complexes are prepared 20 cm(-1) above the dissociation limit is only 1.51 cm(-1), representing only 7.6% of the available energy.