A pulsed-field ionization photoelectron secondary ion coincidence study of the H2+ (X,upsilon+=0-15,N+=1)+He proton transfer reaction

The endothermic proton transfer reaction, H2+(upsilon+)+He-->HeH+ + H(DeltaE=0.806 eV), is investigated over a broad range of reactant vibrational levels using high-resolution vacuum ultraviolet to prepare reactant ions either through excitation of autoionization resonances, or using the pulsed-field ionization-photoelectron-secondary ion coincidence (PFI-PESICO) approach. In the former case, the translational energy dependence of the integral reaction cross sections are measured for upsilon+=0-3 with high signal-to-noise using the guided-ion beam technique. PFI-PESICO cross sections are reported for upsilon+=1-15 and upsilon+=0-12 at center-of-mass collision energies of 0.6 and 3.1 eV, respectively. All ion reactant states selected by the PFI-PESICO scheme are in the N+=1 rotational level. The experimental cross sections are complemented with quasiclassical trajectory (QCT) calculations performed on the ab initio potential energy surface provided by Palmieri et al. [Mol. Phys. 98, 1839 (2000)]. The QCT cross sections are significantly lower than the experimental results near threshold, consistent with important contributions due to resonances observed in quantum scattering studies. At total energies above 2 eV, the QCT calculations are in excellent agreement with the present results. PFI-PESICO time-of-flight (TOF) measurements are also reported for upsilon+=3 and 4 at a collision energy of 0.6 eV. The velocity inverted TOF spectra are consistent with the prevalence of a spectator-stripping mechanism.     

Experimental and theoretical differential cross sections for the N(2D) + H2 reaction

In this paper, we report a combined experimental and theoretical study on the dynamics of the N(2D) + H2 insertion reaction at a collision energy of 15.9 kJ mol(-1). Product angular and velocity distributions have been obtained in crossed beam experiments and simulated by using the results of quantum mechanical (QM) scattering calculations on the accurate ab initio potential energy surface (PES) of Pederson et al. (J. Chem. Phys. 1999, 110, 9091). Since the QM calculations indicate that there is a significant coupling between the product angular and translational energy distributions, such a coupling has been explicitly included in the simulation of the experimental results. The very good agreement between experiment and QM calculations sustains the accuracy of the NH2 ab initio ground state PES. We also take the opportunity to compare the accurate QM differential cross sections with those obtained by two approximate methods, namely, the widely used quasiclassical trajectory calculations and a rigorous statistical method based on the coupled-channel theory.     

A time-dependent wave packet quantum scattering study of the reaction HD+ (v = 0 - 3;j0 = 1) + He --> HeH+(HeD+) + D(H)

Time-dependent wave packet quantum scattering (TWQS) calculations are presented for HD(+) (v = 0 - 3;j(0)=1) + He collisions in the center-of-mass collision energy (E(T)) range of 0.0-2.0 eV. The present TWQS approach accounts for Coriolis coupling and uses the ab initio potential energy surface of Palmieri et al. [Mol. Phys. 98, 1839 (2000)]. For a fixed total angular momentum J, the energy dependence of reaction probabilities exhibits quantum resonance structure. The resonances are more pronounced for low J values and for the HeH(+) + D channel than for the HeD(+) + H channel and are particularly prominent near threshold. The quantum effects are no longer discernable in the integral cross sections, which compare closely to quasiclassical trajectory calculations conducted on the same potential energy surface. The integral cross sections also compare well to recent state-selected experimental values over the same reactant and translational energy range. Classical impulsive dynamics and steric arguments can account for the significant isotope effect in favor of the deuteron transfer channel observed for HD(+)(v<3) and low translational energies. At higher reactant energies, angular momentum constraints favor the proton-transfer channel, and isotopic differences in the integral cross sections are no longer significant. The integral cross sections as well as the J dependence of partial cross sections exhibit a significant alignment effect in favor of collisions with the HD(+) rotational angular momentum vector perpendicular to the Jacobi R coordinate. This effect is most pronounced for the proton-transfer channel at low vibrational and translational energies.     

Real wave packet and quasiclassical trajectory studies of the H+ + LiH reaction

Time-dependent real wave packet (RWP) and quasiclassical trajectory (QCT) calculations have been carried out to study the H(+) + LiH reaction on the ab initio potential-energy surface of Martinazzo et al. [J. Chem. Phys., 2003, 119, 11241]. Total initial state-selected and final state-resolved reaction probabilities for the two possible reaction channels, H(2)(+) + Li and LiH + H(+), have been calculated for total angular momentum J=0 at a broad range of collision energies. Integral cross sections and thermal rate coefficients have been calculated using the QCT method and from the corresponding J=0 RWP reaction probabilities by means of a capture model. The calculated thermal rate coefficients are found to be nearly independent of temperature in the 100-500 K interval with a value of approximately 10(-9) cm(3) s(-1), which is in good agreement with estimates used in evolutionary models of early-Universe lithium chemistry. The RWP results are found to be in good agreement overall with the corresponding QCT calculations.     

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.     

A state-to-state dynamical study of the Br + H(2) reaction: comparison of quantum and classical trajectory results

We present a detailed theoretical investigation of the dynamics corresponding to the strongly endothermic Br + H(2) (v = 0-1, j = 0) → H + HBr reaction in the 0.85 to 1.9 eV total energy range. State-averaged and state-to-state results obtained through time-independent wave packet (TIWP) and time-independent quantum mechanical (TIQM) calculations and quasiclassical trajectories (QCT) are compared and analyzed. The agreement in the results obtained with both quantum mechanical results is very good overall. However, although QCT calculations reproduce the general features, their agreement with the QM results is sometimes only qualitative. The analysis of the mechanism based on state-averaged results turns out to be deceptive and conveys an oversimplified picture of the reaction consistent with a direct-rebound mechanism. Consideration of state-to-state processes, in contrast, unveils the existence of multiple mechanisms that give rise to a succession of maxima in the differential cross section (DCS). Such mechanisms correlate with different sets of partial waves and display similar collision times when analyzed through the time-dependent DCS.     

Quantum mechanical and quasiclassical trajectory scattering calculations for the C(1D) + H2 reaction on the second excited 1 1A" potential energy surface

Time-independent quantum mechanical (QM) and quasiclassical trajectory (QCT) scattering calculations have been carried out for the C(1D) + H2 --> CH + H reaction at a collision energy of 80 meV on a newly developed ab initio potential energy surface [B. Bussery-Honvault et al., Phys. Chem. Chem. Phys. 7, 1476 (2005)] of 1 1A" symmetry, corresponding to the second singlet state 1 1B1 of CH2. A general good agreement has been found between the QM and QCT rotational distributions and differential cross sections (DCSs). In both cases, DCSs are strongly peaked in the forward direction with a small contribution in the backward direction in contrast with those obtained on the 1 1A' surface, which are nearly symmetric. Rotational distributions obtained on the 1 1A" surface are somewhat colder than those calculated on the 1 1A' surface. The specific dynamics and the contribution of the 1 1A" surface to the overall reactivity of this system are discussed.     

Communication: rate coefficients from quasiclassical trajectory calculations from the reverse reaction: The Mu + H2 reaction re-visited

In a previous paper [P. G. Jambrina et al., J. Chem. Phys. 135, 034310 (2011)] various calculations of the rate coefficient for the Mu + H(2) → MuH + H reaction were presented and compared to experiment. The widely used standard quasiclassical trajectory (QCT) method was shown to overestimate the rate coefficients by several orders of magnitude over the temperature range 200-1000 K. This was attributed to a major failure of that method to describe the correct threshold for the reaction owing to the large difference in zero-point energies (ZPE) of the reactant H(2) and product MuH (～0.32 eV). In this Communication we show that by performing standard QCT calculations for the reverse reaction and then applying detailed balance, the resulting rate coefficient is in very good agreement with the other computational results that respect the ZPE, (as well as with the experiment) but which are more demanding computationally.     

Cumulative reaction probabilities: A comparison between quasiclassical and quantum mechanical results

This article presents a quasiclassical trajectory (QCT) method for determining the cumulative reaction probability (CRP) as a function of the total energy. The method proposed is based on a discrete sampling using integer values of the total and orbital angular momentum quantum numbers for each trajectory and on the development of equations that have a clear counterpart in the quantum mechanical (QM) case. The calculations comprise cumulative reaction probabilities at a given total angular momentum J, as well as those summed over J. The latter are used to compute QCT rate constants. The method is illustrated by comparing QCT and exact QM results for the H+H2, H+D2, D+H2, and H+HD reactions. The agreement between QCT and QM results is very good, with small discrepancies between the two data sets indicating some genuine quantum effects. The most important of these involves the value of the CRP at low energies which, due to the absence of tunneling, is lower in the QCT calculations, causing the corresponding rate constants to be smaller. The second is the steplike structure that is clearly displayed in the QM CRP for J = 0, which is much smoother in the corresponding QCT results. However, when the QCT density of reactive states, i.e., the derivatives of the QCT CRP with respect to the energy, is calculated, a succession of maxima and minima is obtained which roughly resembles those found in the QM calculations, although the latter are considerably sharper. The analysis of the broad peaks in the QCT density of reactive states indicates that the distributions of collision times associated with the maxima are somewhat broader, with a tail extending to larger collision times, than those associated with the minima. In addition, the QM and QCT dynamics of the isotopic variants mentioned above are compared in the light of their CRPs. Issues such as the compliance of the QCT CRP with the law of microscopic reversibility, as well as the similarity between the CRPs for ortho and para species in the QM and QCT cases, are also addressed.     

An experimental and quasiclassical trajectory study of the rovibrationally state-selected reactions: HD+(v=0-15,j=1)+He-->HeH+(HeD+)+D(H)

The absolute integral cross sections for the formation of HeH+ and HeD+ from the collisions of HD+(v,j=1)+He have been examined over a broad range of vibrational energy levels v=0-13 at the center-of-mass collision energies (ET) of 0.6 and 1.4 eV using the vacuum ultraviolet (VUV) pulsed field ionization photoelectron secondary ion coincidence method. The ET dependencies of the integral cross sections for products HeH+ and HeD+ from HD+(v=0-4)+He collisions in the ET range of 0-3 eV have also been measured using the VUV photoionization guided ion beam mass spectrometric technique, in which vibrationally selected HD+(v) reactant ions were prepared via excitation of selected autoionization resonances of HD. At low total energies, a pronounced isotope effect is observed in absolute integral cross sections for the HeH++D and HeD++H channels with significant favoring of the deuteron transfer channel. As v is increased in the range of v=0-9, the integral cross sections of the HeH++D channel are found to approach those of HeD++H. The observed velocity distributions of products HeD+ and HeH+ are consistent with an impulsive or spectator-stripping mechanism. Detailed quasiclassical trajectory (QCT) calculations are also presented for HD+(v,j=1)+He collisions at the same energies of the experiment. The QCT calculations were performed on the most accurate ab initio potential energy surface available. If the zero-point energy of the reaction products is taken into account, the QCT cross sections for products HeH+ and HeD+ from HD+(v)+He are found to be significantly lower than the experimental results at ET values near the reaction thresholds. The agreement between the experimental and QCT cross sections improves with translational energy. Except for prethreshold reactivity, QCT calculations ignoring the zero-point energy in the products are generally in good agreement with experimental absolute cross sections. The experimental HeH+/HeD+ branching ratios for the HD+(v=0-9)+He collisions are generally consistent with QCT predictions. The observed isotope effects can be rationalized on the basis of differences in thermochemical thresholds and angular momentum conservation constraints.     

Ab initio analytical potential energy surface and quasiclassical trajectory study of the O(+)((4)S)+H(2)(X (1)Sigma(g) (+))-->OH(+)(X (3)Sigma(-))+H((2)S) reaction and isotopic variants

An analytical potential energy surface (PES) representation of the O(+)((4)S)+H(2)(X (1)Sigma(g) (+)) system was developed by fitting around 600 CCSD(T)/cc-pVQZ ab initio points. Rate constant calculations for this reaction and its isotopic variants (D(2) and HD) were performed using the quasiclassical trajectory (QCT) method, obtaining a good agreement with experimental data. Calculations conducted to determine the cross section of the title reaction, considering collision energies (E(T)) below 0.3 eV, also led to good accord with experiments. This PES appears to be suitable for kinetics and dynamics studies. Moreover, the QCT results show that, although the hypotheses of a widely used capture model are not satisfied, the resulting expression for the cross section can be applied within a suitable E(T) interval, due to errors cancellation. This could be a general situation regarding the application of this simple model to ion-molecule processes.     

Molecular beam scattering studies of the reaction D + H2 (v = 0) and D + H2 (v = 1) → HD + H

The reaction D + H₂ → HD + H has been investigated in two molecular beam scattering experiments. Angular and time-of-flight distributions have been measured for the initial vibrational ground state (v = 0) at a most probable collision energy of E_cm = 1.5 eV and for the first vibrational excited state (v = 1) at E_cm = 0.28 eV with the same apparatus. Results for the ground-state experiment are compared with quasiclassical trajectory calculations(QCT) on the LSTH-hypersurface transformed into the laboratory system and averaged over the apparatus distributions. The agreement isquite satisfactory. At this high collision energy the HD products are no longer scattered in a backward direction but in a wide angular region concentrated about θ = 90° in the center-of-mass system. The absolute reactive cross section has been determined and the agreement with the theoretical value from QCT calculations is within the experimental error. The high sensitivity of the experiment to different properties of the doubly differential cross section has also been demonstrated. A preliminary evaluation of the experiment with initial vibrational excitation (v = 1) shows that the HD-product molecules are preferably backward scattered and the change of internal energy is small supporting the concept of a reaction which is adiabatic with respect to the internal degrees of freedom.     

Corroboration of theory for H + D2 --> D + HD (v' = 3, j' = 0) reactive scattering dynamics

The differential cross section (DCS) for the reaction H + D2 --> D + HD (v' = 3, j' = 0) exhibits particularly rich dynamics; in addition to the expected direct recoil backscattering feature, a surprising time-delayed forward scattering feature appears that has been attributed to glory scattering arising from nearside and farside interference. This fact leads to a complex DCS that depends strongly on the collision energy. Its accurate calculation requires a fully quantum mechanical (QM) treatment. We report improved measurements of this DCS over the collision energy range 1.55 < or = E(coll) < or = 1.82 eV. Previous measurements using the core extraction method, while generally in agreement with theory, lacked sufficient resolution to capture all of the noteworthy behavior of the system; in the present work, we use ion imaging to observe many previously unresolved features of the DCS, particularly in the forward-scattered region. Agreement with QM calculations is found at all collision energies, reconciling an earlier discrepancy between experiment and theory near E(coll) = 1.54 eV.     

Cross sections of the O+ + H2 --> OH+ + H ion-molecule reaction and isotopic variants (D2, HD): quasiclassical trajectory study and comparison with experiments

A dynamics study [cross section and microscopic mechanism versus collision energy (E(T))] of the reaction O+ + H2 --> OH+ + H, which plays an important role in Earth's ionosphere and interstellar chemistry, was conducted using the quasiclassical trajectory method, employing an analytical potential energy surface (PES) recently derived by our group [R. Martinez et al., J. Chem. Phys. 120, 4705 (2004)]. Experimental excitation functions for the title reaction, as well as its isotopic variants with D2 and HD, were near-quantitatively reproduced in the calculations in the very broad collision energy range explored (E(T) = 0.01-6.0 eV). Intramolecular and intermolecular isotopic effects were also examined, yielding data in good agreement with experimental results. The reaction occurs via two microscopic mechanisms (direct and nondirect abstraction). The results were satisfactorily interpreted based on the reaction probability and the maximum impact parameter dependences with E(T), and considering the influence of the collinear [OHH]+ absolute minimum of the PES on the evolution from reactants to products. The agreement between theory and experiment suggests that the reaction mainly occurs through the lowest energy PES and nonadiabatic processes are not very important in the wide collision energy range analyzed. Hence, the PES used to describe this reaction is suitable for both kinetics and dynamics studies.     

辛准经典轨迹法研究Cl+H2反应

用辛准经典轨迹法模拟了Cl+H2反应在mBW2势能面上的动力学行为。研究了各种初始条件下的反应碰撞截面,产物的能量分配,角度分布和态分布。另外,我们还比较了反应物的三种能量形式(平动能,转动能和振动能)对反庆的有效性。     

Exact quantum dynamics study of the O(+)+H2(v=0,j=0)-->OH(+)+H ion-molecule reaction and comparison with quasiclassical trajectory calculations

The close-coupling hyperspherical (CCH) exact quantum method was used to study the title barrierless reaction up to a collision energy (E(T)) of 0.75 eV, and the results compared with quasiclassical trajectory (QCT) calculations to determine the importance of quantum effects. The CCH integral cross section decreased with E(T) and, although the QCT results were in general quite similar to the CCH ones, they presented a significant deviation from the CCH data within the 0.2-0.6 eV collision energy range, where the QCT method did not correctly describe the reaction probability. A very good accord between both methods was obtained for the OH(+) vibrational distribution, where no inversion of population was found. For the OH(+) rotational distributions, the agreement between the CCH and QCT results was not as good as in the vibrational case, but it was satisfactory in many conditions. The kk(') angular distribution showed a preferential forward character, and the CCH method produced higher forward peaks than the QCT one. All the results were interpreted considering the potential energy surface and plots of a representative sampling of reactive trajectories.     

Cross sections and low temperature rate coefficients for the H + CH+ reaction: a quasiclassical trajectory study

The H + CH(+) reaction is studied by quasiclassical trajectory (QCT) calculations, along with phase space theory (PST) and quantum rigid rotor calculations, employing a global single-valued potential energy surface recently derived by our group. We report QCT total cross sections for each of the three channels, for low collision energies and different reactant rotational quantum numbers. At the lowest collision energies, all cross sections exhibit a capture-like behaviour, as expected from a barrierless reaction. At higher energies, there are important dynamical effects coming from the opening of new channels in the inelastic and reactive exchange collisions. The inelastic cross sections turn out to largely increase, while the reactive abstraction cross sections are declining faster than predicted by the capture theory. A large value of the reactant rotational quantum number tends to suppress these dynamical effects. The QCT rate coefficients are reported for a temperature range from 1-700 K. Below 20 K, the abstraction and exchange QCT rate coefficients are almost constant, as predicted by the capture theory. Above this temperature, the abstraction rate coefficient declines, while the exchange and inelastic rate coefficients are increasing, due to the opening of new channels. A good agreement is observed between the experimental abstraction rate coefficient and the QCT and PST ones. The QCT inelastic results are also compared with those obtained from rigid rotor close coupling (CCRR) calculations in order to check the ability of this approach to provide a reliable estimate of the inelastic rate coefficients for a reactive system without a barrier. The laws of variation as a function of temperature are found to be very similar and the curves are parallel above 20 K. However, reaction is not allowed in the rigid rotor approximation, therefore the CCRR results are about twice as large as their QCT counterparts.     

Cumulative reaction probabilities and transition state properties: a study of the F + H2 reaction and its deuterated isotopic variants

A comparative quantum mechanical (QM) and quasiclassical trajectory (QCT) study of the cumulative reaction probabilities (CRPs) is presented in this work for the F + H(2) reaction and its isotopic variants for low values of the total angular momentum J. The agreement between the two sets of calculations is very good with the exception of some features whose origin is genuinely QM. The agreement also extends to the CRP resolved in the helicity quantum number k. The most remarkable feature is the steplike structure, which becomes clearly distinct when the CRPs are resolved in odd and even rotational states j. The analysis of these steps shows that each successive increment is due to the opening of the consecutive rovibrational states of the H(2) or D(2) molecule, which, in this case, nearly coincide with those of the transition state. Moreover, the height of each step reflects the number of helicity states compatible with a given J and j values, thus indicating that the various helicity states for a specific j have basically the same contribution to the CRPs at a given total energy. As a consequence, the dependence with k of the reactivity is practically negligible, suggesting very small steric restrictions for any possible orientation of the reactants. This behavior is in marked contrast to that found in the D + H(2) reaction, wherein a strong k dependence was found in the threshold and magnitude of the CRP. The advantages of a combined QCT and QM approaches to the study of CRPs are emphasized in this work.